TW201345028A - Composition - Google Patents

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TW201345028A
TW201345028A TW102103465A TW102103465A TW201345028A TW 201345028 A TW201345028 A TW 201345028A TW 102103465 A TW102103465 A TW 102103465A TW 102103465 A TW102103465 A TW 102103465A TW 201345028 A TW201345028 A TW 201345028A
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Taiwan
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composition
carbon
carbon nanostructure
particles
weight
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TW102103465A
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Chinese (zh)
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Mamdouh Elsayed Abdelsalam
Fazlil Coowar
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Nexeon Ltd
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Priority claimed from GB1201541.8A external-priority patent/GB2498803B/en
Priority claimed from GB1201540.0A external-priority patent/GB2498802B/en
Application filed by Nexeon Ltd filed Critical Nexeon Ltd
Publication of TW201345028A publication Critical patent/TW201345028A/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/24—Alkaline accumulators
    • H01M10/28—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2202/00—Structure or properties of carbon nanotubes
    • C01B2202/20—Nanotubes characterized by their properties
    • C01B2202/32—Specific surface area
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2202/00—Structure or properties of carbon nanotubes
    • C01B2202/20—Nanotubes characterized by their properties
    • C01B2202/36—Diameter
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/30—Batteries in portable systems, e.g. mobile phone, laptop
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

A composition comprising at least 50 weight % of a first particulate electroactive material and 3-15 weight % of a carbon additives mixture comprising elongate carbon nanostructures and carbon black, wherein: the elongate carbon nanostructures comprise at least a first elongate carbon nanostructure material and a different second elongate carbon nanostructure material; and the elongate carbon nanostructures: carbon black weight ratio is in the range 3: 1 to 20: 1.

Description

組成物 Composition

本發明係關於包含電活性材料之粒子及添加劑之組成物，及該組成物在包括燃料電池及可充電金屬離子電池等裝置中的用途。 The present invention relates to compositions comprising particles and additives of electroactive materials, and to the use of such compositions in devices including fuel cells and rechargeable metal ion batteries.

可充電金屬-離子電池，例如鋰離子電池，係廣泛地使用在攜帶型電子裝置，諸如行動電話和膝上型電腦，且在電動車或油電混合車上發展出更多的應用。 Rechargeable metal-ion batteries, such as lithium ion batteries, are widely used in portable electronic devices, such as mobile phones and laptops, and have developed more applications on electric vehicles or hybrid vehicles.

可充電金屬離子電池具有可釋放和再注入金屬離子的陽極層和陰極層，及在該陽極和陰極層間的電解質。當電池槽完全充電時，金屬離子係藉由電解質從含有金屬離子的陰極層傳輸到陽極層。在鋰離子電池的石墨基的陽極層之例子中，鋰係與石墨反應以製造化合物LixC6(0≦x≦1)。作為複合陽極層中的電化學活性材料，石墨係具有372 mAh/g之最大容量。 A rechargeable metal ion battery has an anode layer and a cathode layer that can release and re-inject metal ions, and an electrolyte between the anode and cathode layers. When the battery cell is fully charged, the metal ions are transported from the cathode layer containing the metal ions to the anode layer by the electrolyte. In the example of a graphite-based anode layer of a lithium ion battery, lithium is reacted with graphite to produce a compound Li x C 6 (0≦x≦1). As an electrochemically active material in the composite anode layer, the graphite system has a maximum capacity of 372 mAh/g.

亦已知可具有比石墨大的容量之矽基活性陽極材料的用途。 The use of bismuth-based active anode materials which can have a larger capacity than graphite is also known.

WO2009/010758揭示矽粉末的蝕刻以製造用於鋰離子電池的矽材料。 WO 2009/010758 discloses etching of tantalum powder to make a tantalum material for a lithium ion battery.

Xiao等人在J.Electrochem.Soc.,Volume 157,Issue 10,pp.A1047-A1051(2010)，「用於鋰離子電池的矽陽極之穩定化(Stabilization of Silicon Anode for Li-ion Batteries)」中揭示包含矽粒子及碳黑(Ketjenblack carbon)之陽極。 Xiao et al., J. Electrochem. Soc., Volume 157, Issue 10, pp. A1047-A1051 (2010), "Stabilization of Silicon Anode for Li-ion Batteries" An anode comprising cerium particles and carbon black (Ketjenblack carbon) is disclosed.

Lestriez等人在Electrochemical and Solid-State Letters,Vol.12,Issue 4,pp.A76-A80(2009)，「用於高能量Si負電極之橋接碳奈米管及奈米纖維之分層且有彈力的導電網絡(Hierarchical and Resilient Conductive Network of Bridged Carbon Nanotubes and Nanofibers for High-Energy Si Negative Electrodes)」中揭示包含多壁碳奈米管及氣相生長奈米纖維的複合電極。 Lestriez et al., Electrochemical and Solid-State Letters, Vol. 12, Issue 4, pp. A76-A80 (2009), "Layered carbon nanotubes and nanofibers for high energy Si negative electrodes. A composite electrode comprising a multi-walled carbon nanotube and a vapor-grown nanofiber is disclosed in Hierarchical and Resilient Conductive Network of Bridged Carbon Nanotubes and Nanofibers for High-Energy Si Negative Electrodes.

US2011/163274揭示矽的電極複合物、碳奈米管及碳奈米纖維。 US 2011/163274 discloses electrode composites of tantalum, carbon nanotubes and carbon nanofibers.

本發明的一個目標係提供用於可維持高容量之金屬離子電池的陽極組成物。 One object of the present invention is to provide an anode composition for a metal ion battery that can maintain high capacity.

本發明的另一個目標係提供用來自漿液形成金屬離子電池之陽極的組成物。 Another object of the present invention is to provide a composition for forming an anode of a metal ion battery from a slurry.

在第一態樣中，本發明提供一種組成物，其包含至少50重量%之第一微粒電活性材料及至少3-15重量%之包含延長碳奈米結構及碳黑之碳添加劑，其中，該延長碳奈米結構包含至少一種第一延長碳奈米結構材料及一種第二延長碳奈米結構材料，且該延長碳奈米結構：碳黑之重量比係在3：1至20：1的範圍內。 In a first aspect, the present invention provides a composition comprising at least 50% by weight of a first particulate electroactive material and at least 3-15% by weight of a carbon additive comprising an extended carbon nanostructure and carbon black, wherein The extended carbon nanostructure comprises at least one first elongated carbon nanostructure material and a second extended carbon nanostructure material, and the extended carbon nanostructure: carbon black weight ratio is between 3:1 and 20:1 In the range.

視需要，該第一微粒電活性材料為含矽材料。 The first particulate electroactive material is a cerium-containing material, as needed.

視需要，該組成物包含至多80wt%，視需要60-80wt%之第一微粒電活性材料。 If desired, the composition comprises up to 80% by weight, optionally 60-80% by weight of the first particulate electroactive material.

視需要，該第一微粒電活性材料包含具有粒子核心及自粒子核心延伸之電活性柱狀物之粒子。 Optionally, the first particulate electroactive material comprises particles having a particle core and an electroactive pillar extending from the particle core.

視需要，該含矽粒子的柱狀物為矽柱狀物。 The column containing the cerium particles is a columnar column as needed.

視需要，該含矽粒子的核心包含矽。 The core of the cerium-containing particles contains cerium as needed.

視需要，該含矽粒子基本上由n-或p-摻雜矽組成且其中該 柱狀物與核心係構成整體。 The cerium-containing particles consist essentially of n- or p-doped cerium, and wherein The pillars are integral with the core system.

視需要，該第一延長奈米結構具有至少100nm的中數平均直徑(mean average diameter)。 The first extended nanostructure has a mean average diameter of at least 100 nm, as desired.

視需要，該第二延長碳奈米結構材料具有不超過90nm的中數平均直徑，視需要為範圍在40-90nm內的中數平均直徑。 The second elongated carbon nanostructure material has a median average diameter of not more than 90 nm, as needed, and a median average diameter in the range of 40 to 90 nm, as needed.

視需要，該第一延長奈米結構：第二延長奈米結構的重量比係在2.5：1至20：1的範圍內。 The first extended nanostructure: the weight ratio of the second extended nanostructure is in the range of 2.5:1 to 20:1, as needed.

視需要，該等至少第一及第二延長碳奈米結構各自獨立地具有至少為50的縱橫比。 The at least first and second elongated carbon nanostructures each independently have an aspect ratio of at least 50, as desired.

視需要，該等第一及第二碳延長奈米結構材料係各自獨立地選自碳奈米管及碳奈米纖維。 The first and second carbon-extended nanostructure materials are each independently selected from the group consisting of carbon nanotubes and carbon nanofibers, as desired.

視需要，該第一碳延長奈米結構材料為奈米纖維且該第二延長碳奈米結構材料為奈米管。 Optionally, the first carbon extended nanostructure material is a nanofiber and the second elongated carbon nanostructure material is a nanotube.

視需要，該等至少第一及第二延長碳奈米結構材料係以總量在該組成物的0.1-15重量%的範圍內提供。 The at least first and second extended carbon nanostructure materials are provided in a total amount ranging from 0.1 to 15% by weight of the composition, as needed.

視需要，一或多種該等延長碳奈米結構材料具有官能化之表面，視需要為以含氮基團或含氧基團官能化之表面。 If desired, one or more of the extended carbon nanostructured materials have a functionalized surface, optionally a surface functionalized with a nitrogen-containing group or an oxygen-containing group.

視需要，該組成物另外包含石墨。 The composition additionally contains graphite as needed.

視需要，該石墨係以1-30wt%，視需要1-20wt%，視需要1-15wt%，視需要1-12wt%，視需要1-6wt%之量提供於該組成物中。 The graphite is supplied in the composition in an amount of from 1 to 30% by weight, optionally from 1 to 20% by weight, optionally from 1 to 15% by weight, optionally from 1 to 12% by weight, as needed, to 1-6% by weight, as needed.

視需要，該組成物包含3-12重量%之碳添加劑混合物。 The composition contains 3-12% by weight of a carbon additive mixture, as needed.

視需要，該石墨之微晶長度Lc視需要為至少50nm，視需要為至少100nm。 The crystallite length Lc of the graphite is optionally at least 50 nm, if necessary, at least 100 nm, as needed.

視需要，該碳黑係以該組成物的至少0.5wt%，及視需要以該組成物的小於10wt%，視需要以該組成物的小於4wt%的量提供。 The carbon black is provided in an amount of at least 0.5% by weight of the composition, and optionally less than 10% by weight of the composition, as needed, in an amount of less than 4% by weight of the composition, as needed.

在第二態樣中，本發明提供一種金屬-離子電池，其包含陽極、陰極及在該陽極和該陰極間的電解質，其中該陽極包含根據第一態樣之組成物。 In a second aspect, the invention provides a metal-ion battery comprising an anode, a cathode, and an electrolyte between the anode and the cathode, wherein the anode comprises a composition according to the first aspect.

在第三態樣中，本發明提供一種漿液，其包含根據第一態樣之組成物及至少一種溶劑。 In a third aspect, the invention provides a slurry comprising a composition according to a first aspect and at least one solvent.

在第四態樣中，本發明提供一種形成根據第二態樣之金屬-離子電池之方法，該方法包含藉由將根據第三態樣之漿液沉積於導電材料且蒸發該至少一種溶劑以形成陽極之步驟。 In a fourth aspect, the present invention provides a method of forming a metal-ion battery according to a second aspect, the method comprising forming by depositing a slurry according to a third aspect on a conductive material and evaporating the at least one solvent The step of the anode.

在第五態樣中，本發明提供一種組成物，其包含微粒電活性材料、第一延長碳奈米結構材料及第二延長碳奈米結構材料，其中該第一延長碳奈米結構材料具有至少100nm的中數平均直徑，該第二延長碳奈米結構材料具有小於90nm的中數平均直徑，且其中該第一微粒電活性材料包含具有粒子核心及自粒子核心延伸之電活性材料之柱狀物的粒子。 In a fifth aspect, the present invention provides a composition comprising a particulate electroactive material, a first elongated carbon nanostructure material, and a second elongated carbon nanostructure material, wherein the first elongated carbon nanostructure material has a median average diameter of at least 100 nm, the second elongated carbon nanostructure material having a median average diameter of less than 90 nm, and wherein the first particulate electroactive material comprises a column having a particle core and an electroactive material extending from the particle core Particles.

該第五態樣之組成物的第一微粒電活性材料、第一延長碳奈米結構材料及第二延長碳奈米結構材料可選自本文描述之材料，包括第一態樣中所描述者，且可以本文描述之重量百分比及/或比例提供，包括第一態樣中所描述者。第五態樣的組成物可包含一或多種其他組分，例如黏結劑、碳黑及/或石墨，且該一或多種其他組分可以本文描述之重量百分比及/或比例提供，包括第一態樣中所描述者。 The first particulate electroactive material, the first elongated carbon nanostructure material, and the second extended carbon nanostructure material of the composition of the fifth aspect may be selected from the materials described herein, including those described in the first aspect. And may be provided in weight percentages and/or ratios as described herein, including those described in the first aspect. The fifth aspect of the composition may comprise one or more other components, such as a binder, carbon black and/or graphite, and the one or more other components may be provided in weight percentages and/or ratios as described herein, including first The person described in the aspect.

在第六態樣中，本發明提供一種組成物，其包含第一微粒電活性材料、第一延長碳奈米結構材料及第二延長碳奈米結構材料，其中該第一延長碳奈米結構材料具有至少100nm的中數平均直徑，且該第二延長碳奈米結構材料具有範圍在40-90nm內的中數平均直徑。 In a sixth aspect, the present invention provides a composition comprising a first particulate electroactive material, a first elongated carbon nanostructure material, and a second elongated carbon nanostructure material, wherein the first elongated carbon nanostructure The material has a median average diameter of at least 100 nm, and the second extended carbon nanostructure material has a median average diameter ranging from 40 to 90 nm.

該第六態樣之組成物的第一微粒電活性材料、第一延長碳奈米結構材料及第二延長碳奈米結構材料可選自根據第一態樣描述之材料， 且可以本文描述之重量百分比及/或比例提供，包括第一態樣中所描述者。第六態樣的組成物可包含一或多種其他組分，例如本文描述之黏結劑、碳黑及/或石墨，包括第一態樣中所描述者，且該一或多種其他組分可以本文描述之重量百分比及/或比例提供，包括第一態樣中所描述者。 The first particulate electroactive material, the first elongated carbon nanostructure material, and the second extended carbon nanostructure material of the composition of the sixth aspect may be selected from the materials described according to the first aspect, It can be provided in weight percentages and/or ratios as described herein, including those described in the first aspect. The sixth aspect of the composition may comprise one or more other components, such as the binders, carbon black and/or graphite described herein, including those described in the first aspect, and the one or more other components may be herein The weight percentages and/or ratios provided are provided, including those described in the first aspect.

在第七態樣中，本發明提供一種組成物，其包含黏結劑、第一微粒電活性材料及碳添加劑，該碳添加劑包含第一延長碳奈米結構材料、第二延長碳奈米結構材料、石墨及碳黑。 In a seventh aspect, the present invention provides a composition comprising a binder, a first particulate electroactive material, and a carbon additive, the carbon additive comprising a first elongated carbon nanostructure material and a second elongated carbon nanostructure material , graphite and carbon black.

該第七態樣之組成物的第一微粒電活性材料、第一延長碳奈米結構材料、第二延長碳奈米結構材料、黏結劑、碳黑及石墨可選自本文描述任何地方之材料，包括根據第一態樣描述之材料，且可以本文描述之重量百分比及/或比例提供，包括第一態樣中所描述者。 The first particulate electroactive material, the first elongated carbon nanostructure material, the second extended carbon nanostructure material, the binder, the carbon black, and the graphite of the composition of the seventh aspect may be selected from materials described anywhere herein. , including materials according to the first aspect, and may be provided in weight percentages and/or ratios as described herein, including those described in the first aspect.

在第八態樣中，本發明提供一種組成物，其包含黏結劑、第一微粒電活性材料及碳奈米結構添加劑，該碳奈米結構添加劑包含第一延長碳奈米結構材料、第二延長碳奈米結構材料及視需要碳黑，其中該碳奈米結構添加劑形成不多於10重量%之該組成物。 In an eighth aspect, the present invention provides a composition comprising a binder, a first particulate electroactive material, and a carbon nanostructure additive, the carbon nanostructure additive comprising a first elongated carbon nanostructure material, and a second The carbon nanostructure material and optionally carbon black are extended, wherein the carbon nanostructure additive forms no more than 10% by weight of the composition.

該第八態樣之組成物的黏結劑、第一微粒電活性材料、第一延長碳奈米結構材料、第二延長碳奈米結構材料及碳黑可選自本文描述的材料，包括第一態樣中所描述者，且可以本文描述之重量百分比及/或比例提供，包括第一態樣中所描述者，其限制條件為該碳奈米結構添加劑形成不多於10重量%之該組成物。第八態樣的組成物可包含一或多種其他組分，例如本文描述之石墨，包括第一態樣中所描述者，且該一或多種其他組分可以本文描述之重量百分比及/或比例提供，包括第一態樣中所描述者。 The binder of the composition of the eighth aspect, the first particulate electroactive material, the first elongated carbon nanostructure material, the second extended carbon nanostructure material, and the carbon black may be selected from the materials described herein, including the first It is described in the aspects, and may be provided in weight percentages and/or ratios as described herein, including those described in the first aspect, with the proviso that the carbon nanostructure additive forms no more than 10% by weight of the composition. Things. The eighth aspect of the composition may comprise one or more other components, such as the graphite described herein, including those described in the first aspect, and the one or more other components may be weight percentages and/or ratios as described herein. Provided, including those described in the first aspect.

在第九態樣中，本發明提供一種組成物，其包含黏結劑、第一微粒電活性材料及至少一種延長碳奈米結構材料，其中該延長碳奈米結構材料具有官能化之表面。 In a ninth aspect, the present invention provides a composition comprising a binder, a first particulate electroactive material, and at least one extended carbon nanostructure material, wherein the extended carbon nanostructure material has a functionalized surface.

視需要根據第九態樣，該組成物包含至少兩種延長碳奈米結構材料。該第九態樣中之延長碳奈米結構材料中的一者可為奈米管，且另一者可為奈米纖維。 According to a ninth aspect, the composition comprises at least two elongated carbon nanostructure materials as needed. One of the extended carbon nanostructure structural materials in the ninth aspect may be a nanotube, and the other may be a nanofiber.

該第九態樣之組成物的黏結劑、第一微粒電活性材料及至少一種或至少兩種延長碳奈米結構材料可選自本文描述的材料，包括第一態樣中所描述者，且可以本文描述之重量百分比及/或比例提供，包括第一態樣中所描述者。第九態樣的組成物可包含一或多種其他組分，例如本文描述之碳黑及/或石墨，包括第一態樣中所描述者，且該一或多種其他組分可以本文描述之重量百分比及/或比例提供，包括第一態樣中所描述者。 The binder of the ninth aspect of the composition, the first particulate electroactive material, and the at least one or at least two extended carbon nanostructure materials can be selected from the materials described herein, including those described in the first aspect, and It can be provided in weight percentages and/or ratios as described herein, including those described in the first aspect. The ninth aspect of the composition may comprise one or more other components, such as carbon black and/or graphite as described herein, including those described in the first aspect, and the one or more other components may be weights as described herein. Percentages and/or ratios are provided, including those described in the first aspect.

該第五至第九態樣的組成物可呈漿液提供，且可用於形成能量儲存裝置，例如本文描述的可充電金屬離子電池，包括第一態樣中所描述者。 The fifth to ninth aspect of the composition can be provided as a slurry and can be used to form an energy storage device, such as the rechargeable metal ion battery described herein, including those described in the first aspect.

本文描述的組成物中組分的重量百分比係該等組分在含有所有該組成物的該等組分之多孔或非多孔固體組成物中的重量百分比。在包含組成物的漿液的例子中，應了解該漿液的一或多種溶劑的重量並不形成本文描述的該組成物重量的一部分。 The weight percent of the components in the compositions described herein are the weight percent of the components in the porous or non-porous solid composition of the components containing all of the composition. In the case of a slurry comprising a composition, it will be appreciated that the weight of one or more solvents of the slurry does not form part of the weight of the composition described herein.

關於該等圖式，本發明將更仔細描述，其中：圖1圖形例示根據本發明一個具體實例的金屬離子電池；圖2圖形例示根據本發明一個具體實例的複合電極；圖3A圖形例示藉由蝕刻製程形成柱狀粒子的方法；圖3B圖形例示藉由在核心生長柱狀物形成柱狀粒子的方法；圖4A係根據本發明一個具體實例的組成物的掃描式電子顯微鏡圖像； 圖4B係圖4A圖像一個區域的放大圖；圖4C係圖4B圖像一個區域的放大圖；圖5例示對於根據本發明具體實例的電池及比較裝置之特定放電容量作為循環數及電池電極容量密度mAh/cm-2產物的函數的變化；圖6A例示對於根據本發明具體實例的電池之電極容量密度隨循環數的變化；圖6B例示對於圖6A的電池之充電終止電壓隨循環數的變化；圖7A例示對於根據本發明具體實例的電池之電極容量密度隨循環數的變化；圖7B例示對於圖7A的電池之充電終止電壓隨循環數的變化；圖8-10例示對於根據本發明其他具體實例的電池之電極容量密度mAh/cm-2隨循環數的變化。 The invention will be described more closely with respect to the drawings, wherein: Figure 1 is a diagram illustrating a metal ion battery in accordance with an embodiment of the present invention; Figure 2 is a diagram illustrating a composite electrode in accordance with one embodiment of the present invention; a method of forming columnar particles by an etching process; FIG. 3B is a view illustrating a method of forming columnar particles by growing a pillar in a core; FIG. 4A is a scanning electron microscope image of a composition according to an embodiment of the present invention; FIG. FIG. 4A is an enlarged view of an area of the image of FIG. 4A; FIG. 5 is an enlarged view of a region of the image of FIG. 4B; FIG. 5 illustrates a specific discharge capacity of the battery and the comparison device according to an embodiment of the present invention as a cycle number and a battery electrode capacity density. a change in the function of the mAh/cm -2 product; FIG. 6A illustrates a change in electrode capacity density with cycle number for a battery according to an embodiment of the present invention; FIG. 6B illustrates a change in charge termination voltage with cycle number for the battery of FIG. 6A; 7A illustrates changes in electrode capacity density with cycle number for a battery according to an embodiment of the present invention; FIG. 7B illustrates charge for the battery of FIG. 7A End voltage changes with the number of cycles; -2 Figures 8-10 illustrate variations for a battery electrode according to the present invention, another specific example of the capacity density mAh / cm with the number of cycles.

可充電金屬離子電池槽的結構係顯示於圖1，其並沒有敘明比例尺。電池槽包括單一電池，但亦包括多於一個電池。該電池較佳係鋰離子電池，但也可以是另一金屬離子電池，例如鈉離子及鎂離子。 The structure of the rechargeable metal ion battery cell is shown in Figure 1, which is not to scale. The battery bay includes a single battery but also includes more than one battery. The battery is preferably a lithium ion battery, but may be another metal ion battery such as sodium ions and magnesium ions.

電池槽包括陽極之電流收集器10，例如銅，及陰極之電流收集器12，例如鋁，其皆適當地外部連接至負載或再充電源。包含活性矽粒子14之複合陽極層覆蓋該電流收集器10且含金屬氧化物基的複合陰極層16覆蓋該電流收集器12(為避免任何疑義，本說明書中使用之術語「陽極」及「陰極」如同在將電池槽跨越負載安置之情形下所使用之術語，亦即負極表示陽極且正極表示陰極。本說明書中使用之術語「活性材料」或「電活性材料」應理解為意謂在電池槽充電階段及放電階段期間能夠在結構中 併入並實質上自其中釋放諸如鋰、鈉、鉀、鈣或鎂之金屬離子電荷載流子的材料。該材料較佳能夠併入並釋放鋰。較佳活性材料係在其表面包括具有矽表面之材料，例如矽粒子或具有非矽核心及部分或全部為矽表面之表面的材料之複合物)。 The battery well includes an anode current collector 10, such as copper, and a cathode current collector 12, such as aluminum, which are suitably externally connected to a load or recharge source. A composite anode layer comprising active cerium particles 14 covers the current collector 10 and a metal oxide based composite cathode layer 16 covers the current collector 12 (for the avoidance of any doubt, the terms "anode" and "cathode" are used in this specification. As the term is used in the case where the battery cell is placed across the load, that is, the negative electrode represents the anode and the positive electrode represents the cathode. The term "active material" or "electroactive material" as used in this specification shall be understood to mean a battery. Can be in the structure during the tank charging phase and the discharging phase A material that incorporates and substantially releases metal ion charge carriers such as lithium, sodium, potassium, calcium or magnesium therefrom. The material is preferably capable of incorporating and releasing lithium. Preferably, the active material comprises a material having a ruthenium surface on its surface, such as a ruthenium particle or a composite of a material having a non-ruthenium core and a surface which is partially or wholly a ruthenium surface.

該陰極12包含可釋放及再吸收鋰離子的材料，該鋰離子為例如鋰基金屬氧化物或磷酸鹽、LiCoO2、LiNi0.8Co0.15Al0.05O2、LiMnxNixCo1-2xO2或LiFePO4。 The cathode 12 comprises a material capable of releasing and reabsorbing lithium ions, such as lithium-based metal oxide or phosphate, LiCoO 2 , LiNi 0.8 Co 0.15 Al 0.05 O 2 , LiMn x Ni x Co 1-2x O 2 . Or LiFePO 4 .

液體電解質可在陽極和陰極間提供。在圖1之實例中，多孔塑膠間隔器或分離器20係提供於陽極層14與含鋰陰極層16之間，且液體電解質材料分散於多孔塑膠間隔器或分離器20、複合陽極層14及複合陰極層16內。多孔塑膠間隔器或分離器20可用聚合物電解質材料替換，且在此等情況下聚合物電解質材料存在於複合陽極層14及複合陰極層16兩者內。該聚合物電解質材料可為固體聚合物電解質或凝膠型聚合物電解質。 A liquid electrolyte can be provided between the anode and the cathode. In the example of FIG. 1, a porous plastic spacer or separator 20 is provided between the anode layer 14 and the lithium-containing cathode layer 16, and the liquid electrolyte material is dispersed in the porous plastic spacer or separator 20, the composite anode layer 14 and Inside the composite cathode layer 16. The porous plastic spacer or separator 20 can be replaced with a polymer electrolyte material, and in this case the polymer electrolyte material is present in both the composite anode layer 14 and the composite cathode layer 16. The polymer electrolyte material may be a solid polymer electrolyte or a gel type polymer electrolyte.

當將電池槽電池充滿時，鋰已經由電解質自含鋰金屬氧化物陰極層16傳輸至陽極層14中。 When the battery cell is fully charged, lithium has been transported from the lithium-containing metal oxide cathode layer 16 into the anode layer 14 by the electrolyte.

根據本發明一具體實例之組成物包含含矽粒子、黏結劑及一或多種添加劑。各添加劑較佳係導電材料。各添加劑可為或不為活性材料。 A composition according to an embodiment of the present invention comprises cerium-containing particles, a binder, and one or more additives. Each additive is preferably a conductive material. Each additive may or may not be an active material.

含矽粒子可為結構化粒子。結構化粒子的一種形式為具有核心的粒子，其可包含或不包含矽，該含矽之柱狀物自該核心延伸。結構化粒子的另一種形式係多孔矽，特別是大孔矽，如下列所進一步描述。 The cerium-containing particles can be structured particles. One form of structured particle is a particle having a core that may or may not contain ruthenium, the ruthenium containing pillar extending from the core. Another form of structured particles is porous tantalum, particularly macroporous, as further described below.

添加劑可選自：第一延長碳奈米結構、一或多種其他延長碳奈米結構、碳黑粒子，包括乙炔碳及碳黑(ketjen black)粒子，及包含石墨或石墨烯粒子的材料。各延長碳奈米結構較佳係選自奈米管及奈米纖維。本文所用之「奈米結構」材料可意指包含具有至少小於1微米，較佳小於500nm，更佳小於200nm的尺寸之材料。 The additive may be selected from the group consisting of a first extended carbon nanostructure, one or more other extended carbon nanostructures, carbon black particles, including acetylene carbon and ketjen black particles, and materials comprising graphite or graphene particles. Preferably, each extended carbon nanostructure is selected from the group consisting of a nanotube and a nanofiber. As used herein, "nanostructure" material may mean a material comprising a size having at least less than 1 micron, preferably less than 500 nm, more preferably less than 200 nm.

關於圖2，其並沒有敘明比例尺，本發明一個具體實例之組成物包含含矽粒子201、第一延長奈米結構203、第二延長奈米結構205、碳黑粒子207、石墨粒子209及黏結劑211。圖2所例示之該含矽粒子201為柱狀粒子，其具有自粒子核心延伸之柱狀物，然而，該等含矽粒子可帶有或不帶有柱狀物。 Regarding FIG. 2, the scale is not described. The composition of one embodiment of the present invention comprises cerium-containing particles 201, a first elongated nanostructure 203, a second elongated nanostructure 205, carbon black particles 207, graphite particles 209, and Adhesive 211. The cerium-containing particles 201 illustrated in Fig. 2 are columnar particles having pillars extending from the core of the particles, however, the cerium-containing particles may or may not have pillars.

第二延長奈米結構材料會捲入該等柱狀矽粒子的柱狀物中，且各奈米結構會繞著一些或全部一或多種柱狀矽粒子核心的周圍纏繞，且因此可延伸導電性超出柱狀粒子表面及/或降低柱狀粒子表面和其他導電物種的導電屏障，包括黏結劑和其他陽極添加劑。該第二延長奈米結構亦可捲入其他組成物的組分中，例如石墨(若存在的話)。 The second elongated nanostructure material is entrained in the pillars of the columnar tantalum particles, and each nanostructure is wound around some or all of the one or more columnar tantalum particle cores, and thus the conductive material is extendable Exceeding the surface of the columnar particles and/or reducing the conductive barrier of the surface of the columnar particles and other conductive species, including binders and other anode additives. The second extended nanostructure can also be incorporated into components of other compositions, such as graphite, if present.

該等含矽粒子201的柱狀物或其他結構元素可提供第二延長奈米結構材料205的奈米纖維或奈米管的支撐物。 The pillars or other structural elements of the cerium-containing particles 201 may provide a support for the nanofibers or nanotubes of the second elongated nanostructure material 205.

第一延長奈米結構材料203更大的直徑可使其比第二延長奈米結構材料205更剛硬。該第一延長奈米結構材料203可在組成物內提供沿著各奈米結構長度延伸之導電途徑。該等導電途徑可形成用於介於含矽粒子201間的導電橋聯及介於含矽粒子201和其他複合物中的組分，例如石墨粒子209，的網絡或支撐。 The larger diameter of the first elongated nanostructure material 203 may make it stiffer than the second elongated nanostructure material 205. The first elongated nanostructure material 203 can provide a conductive pathway extending along the length of each nanostructure within the composition. The electrically conductive pathways may form a network or support for conductive bridging between the cerium-containing particles 201 and components interposed between the cerium-containing particles 201 and other composites, such as graphite particles 209.

本發明之組成物可包括僅兩種不同之延長奈米結構材料，例如圖2所例示，或可包括三種或更多不同延長奈米結構材料。 The compositions of the present invention may comprise only two different elongated nanostructure materials, such as illustrated in Figure 2, or may include three or more different elongated nanostructure materials.

含矽粒子 Antimony particles

該等含矽粒子可為結構化粒子。結構化粒子包括具有核心和延伸自該核心的柱狀物之粒子，及在粒子表面上具有孔或在整個粒子體積具有孔的粒子。大孔粒子的表面可在粒子表面，其在該材料內可具有至少50nm尺寸的間隔、空隙或通道，具有該粒子材料實質上連續的網絡，該等空隙可存在粒子體積整體或可限制在粒子的區塊。一個粒子可具有柱狀物 的區塊及孔隙的區塊。該等柱狀物本身可為微孔或中孔的。 The cerium-containing particles can be structured particles. The structured particles include particles having a core and pillars extending from the core, and particles having pores on the surface of the particles or having pores throughout the particle volume. The surface of the macroporous particles may be on the surface of the particles, which may have spaces, voids or channels of at least 50 nm in the material, having a substantially continuous network of such particulate materials, which may exist as a whole or may be confined to the particles. Block. One particle can have a column Blocks and pore blocks. The pillars themselves may be microporous or mesoporous.

本發明組成物中的含矽粒子可實質上由n-或p-摻雜矽組成或可包含一或多種其他材料。例如，在柱狀粒子的例子中，該粒子可選自下列之一者：-具有矽核心之粒子，該矽核心具有延伸自且與該矽核心構成整體的柱狀物；-具有導電材料非矽核心之粒子，例如石墨核心，其具有延伸自該核心的柱狀物；-具有導電材料非矽核心之粒子，例如石墨核心，其係以係殼層塗布且具有延伸自且與該矽殼層構成整體的矽柱狀物。 The cerium-containing particles in the compositions of the present invention may consist essentially of n- or p-doped cerium or may comprise one or more other materials. For example, in the case of a columnar particle, the particle may be selected from one of the following: a particle having a ruthenium core having a pillar extending from and integral with the ruthenium core; a core particle, such as a graphite core, having a pillar extending from the core; a particle having a non-iridium core of a conductive material, such as a graphite core, coated with a shell layer and having an extension from and to the shell The layers constitute an integral column.

該等柱狀物可為核殼結構，內層核心係與外層殼層材料不同之材料，且該核心及/或殼層包含矽。在核心及柱狀物為不同材料的例子中，核心可為或不為電活性材料。 The pillars may be core-shell structures, the inner core layer is different from the outer shell material, and the core and/or shell layer comprises niobium. In the case where the core and the pillars are of different materials, the core may or may not be an electroactive material.

圖3A例示形成柱狀粒子的第一方法，其中起始材料係經蝕刻已形成柱狀粒子，其中起始材料301係暴露於蝕刻調配物以在該起始材料的表面上進行選擇性蝕刻以製造具有核心305及柱狀物307的柱狀粒子303。 3A illustrates a first method of forming columnar particles, wherein the starting material is etched to form columnar particles, wherein the starting material 301 is exposed to an etchant to selectively etch on the surface of the starting material. Columnar particles 303 having a core 305 and pillars 307 are produced.

可查覺到該以此方法形成的柱狀粒子之粒子核心的體積係小於起始材料的體積，且該核心的表面係與該等柱狀物構成整體。該柱狀粒子的大小可與起始材料相同或小於起始材料。 It can be observed that the volume of the particle core of the columnar particles formed by this method is smaller than the volume of the starting material, and the surface of the core is integral with the pillars. The columnar particles may be the same size as or smaller than the starting material.

蝕刻在其表面上具有矽的材料之合適方法係為金屬輔助的化學蝕刻(或稱作電交換腐蝕(galvanic exchange etching)或電腐蝕)，其包含以氟化氫、金屬離子源(例如銀或銅)處理該起始材料，該金屬離子源非電鍍沉積在該矽的表面及氧化物上，例如硝酸鹽離子源。更詳細的合適蝕刻方法可在例如Huang et al.,Adv.Mater.23,pp 285-308(2011)中找到。 A suitable method of etching a material having germanium on its surface is metal assisted chemical etching (or galvanic exchange etching or electrocorrosion) comprising hydrogen fluoride, a source of metal ions (eg, silver or copper). The starting material is treated and the metal ion source is electrolessly deposited on the surface of the crucible and on the oxide, such as a source of nitrate ions. A more detailed suitable etching method can be found, for example, in Huang et al., Adv. Mater. 23, pp 285-308 (2011).

蝕刻方法可包含兩步驟，包括其中金屬係在起始材料的矽表面上形成的步驟及蝕刻步驟。需要可還原的離子的存在來進行蝕刻步驟。例示性的適合此目的之陽離子包括銀的硝酸鹽、鐵(III)、鹼金屬及銨。柱狀物的形成被認為是選擇性地發生在非電鍍沉積金屬下的區塊的蝕刻的結果。 The etching method may comprise two steps, including a step in which a metal is formed on the surface of the crucible of the starting material and an etching step. The presence of reducible ions is required to perform the etching step. Exemplary cations suitable for this purpose include silver nitrates, iron (III), alkali metals, and ammonium. The formation of pillars is believed to be the result of etching of the blocks that selectively occur under the electrolessly deposited metal.

金屬沉積及蝕刻步驟可發生在單一溶液中或可發生在兩種個別的溶液中。 The metal deposition and etching steps can occur in a single solution or can occur in two separate solutions.

在蝕刻方法中所用的金屬可從該反應混合物中回收再使用，特別是如果是貴的金屬，如銀。 The metal used in the etching process can be recovered from the reaction mixture for reuse, especially if it is a noble metal such as silver.

例示性的適合用來形成柱狀粒子的蝕刻方法係揭露於WO2009/010758及WO2010/040985中。 An exemplary etching process suitable for forming columnar particles is disclosed in WO 2009/010758 and WO 2010/040985.

可引入的其他蝕刻方法包括反應性離子蝕刻及其他或學或電化學蝕刻技術，視需要使用蝕刻術來界定該柱狀配置。 Other etching methods that may be introduced include reactive ion etching and other or chemical or electrochemical etching techniques, using etching as needed to define the columnar configuration.

若該柱狀粒子在其核心包含第一材料，即從第二材料形成的殼層，例如以矽塗布之碳，然後該粒子可藉由蝕刻該矽塗布碳至一小於該矽殼層厚度的深度而形成，以形成具有複合碳/矽核心的柱狀粒子。 If the columnar particle comprises a first material in its core, ie a shell layer formed from a second material, such as carbon coated with ruthenium, the particles may then be coated with carbon to a thickness less than the thickness of the ruthenium shell layer by etching the ruthenium. Depth is formed to form columnar particles having a composite carbon/germanium core.

蝕刻可至小於2-10微米，視需要至少0.5微米的深度，以形成具有高至10微米高度的柱狀物。該等柱狀物可具有任何形狀。例如，該等柱狀物可為分枝或未分枝、實質上直的或彎曲的，且有實質上不變的厚度或切斜面。 The etching can be to a depth of less than 2-10 microns, optionally at least 0.5 microns, to form pillars having a height of up to 10 microns. The pillars can have any shape. For example, the pillars can be branched or unbranched, substantially straight or curved, and have a substantially constant thickness or bevel.

該等柱狀物可利用例如生長、吸附或融合柱狀物至核心上或在核心外生長柱狀物的方法形成於粒子核心上或連接至粒子核心。圖3B例示形成柱狀粒子的第二方法，其中柱狀物307、較佳矽柱狀物，例如矽奈米線，係生長在起始材料301上或連接至起始材料301，例如矽或碳(例如，石墨或石墨烯)起始材料。所得到的柱狀粒子303的粒子核心305的體積實質 上可與起始材料301的體積相同。換句話說，起始材料的表面可提供粒子核心305的表面，柱狀物307係自該粒子核心延伸。 The pillars may be formed on the particle core or attached to the particle core by, for example, growing, adsorbing or fusing the pillars onto the core or growing the pillars outside the core. Figure 3B illustrates a second method of forming columnar particles wherein a pillar 307, preferably a columnar column, such as a strontium nanowire, is grown on the starting material 301 or attached to a starting material 301, such as hydrazine or Carbon (eg, graphite or graphene) starting materials. The volumetric essence of the particle core 305 of the obtained columnar particle 303 The upper portion may be the same volume as the starting material 301. In other words, the surface of the starting material can provide the surface of the particle core 305 from which the column 307 extends.

例示性的用來生長柱狀物的方法包括化學氣相沉積(CVD)及流化床反應器利用氣體-液體-固體(VLS)方法。該VLS方法包括在起始材料表面形成液體合金的步驟，其中在表面上生長線，接著以氣體形式引入物質以形成柱狀物，該柱狀物擴散進入液體。在液體/固體介面的過飽合及成核導致垂直晶體生長。用於形成液體合金微滴的催化劑材料可例如包括Au、Ni或Sn。 Exemplary methods for growing pillars include chemical vapor deposition (CVD) and fluidized bed reactors utilizing a gas-liquid-solid (VLS) process. The VLS method includes the step of forming a liquid alloy on the surface of the starting material, wherein a line is grown on the surface, followed by introduction of the substance in the form of a gas to form a column that diffuses into the liquid. Supersaturation and nucleation at the liquid/solid interface results in vertical crystal growth. The catalyst material used to form the liquid alloy droplets may, for example, include Au, Ni or Sn.

奈米線可在起始材料的一或多個表面上生長。 The nanowires can be grown on one or more surfaces of the starting material.

柱狀物亦可在起始材料的表面上製造，其係利用熱漿或雷射消熔方法。 The pillars can also be fabricated on the surface of the starting material using a hot paste or laser ablation process.

該等柱狀物亦可利用例如固體-液體-固體生長技術之方法藉由在起始材料外的奈米線生長而形成。在一個實例中，矽或矽基起始材料小粒係以催化劑粒子(例如Ni)塗布且加熱使得液體合金微滴在表面形成，而氣體係含其他元素引入。氣體誘發含該起始材料及其他來自該氣體的元素之產物的縮合，在該起始材料外製造奈米線的生長。此方法係在所有起始材料被納入奈米線之前終止以製造柱狀粒子。在此方法中，該柱狀粒子的核心將小於起始材料。 The pillars can also be formed by growth of a nanowire outside the starting material by, for example, solid-liquid-solid growth techniques. In one example, the ruthenium or ruthenium-based starting material granules are coated with catalyst particles (eg, Ni) and heated such that liquid alloy droplets form on the surface, while the gas system contains other elements introduced. The gas induces condensation of the product comprising the starting material and other elements from the gas, and the growth of the nanowires is made outside the starting material. This method is terminated before all of the starting materials are incorporated into the nanowire to produce columnar particles. In this method, the core of the columnar particles will be smaller than the starting material.

在起始材料上或在其外生長的矽柱狀物可以未摻雜矽生長，或其可藉由在奈米線生長期間或在後生長製程步驟期間引入掺雜物來摻雜。 The pillars grown on or outside the starting material may be grown undoped, or they may be doped by introducing dopants during nanowire growth or during a post-growth process step.

該等柱狀物係在該核心的表面間隔開來。在一配置中，所有柱狀物實質上可間隔開。在另一配置中，一些柱狀物可簇擁在一起。 The pillars are spaced apart on the surface of the core. In one configuration, all of the pillars are substantially spaced apart. In another configuration, some of the pillars can be clustered together.

粒子核心的起始材料較佳係呈微粒形式，例如粉末，且該起始材料的粒子可具有任何形狀。例如，起始材料粒子可為立方形(cuboid)、 類立方形(cuboidal)、實質上為球形(spherical)或類球形(spheroid)、像薄片的形狀。粒子表面可為光滑的、粗糙的或有角的且該等粒子可為多面(multi-faceted)或具有單一連續的曲線表面。該等粒子可為多孔或非多孔的。 The starting material of the particle core is preferably in the form of particles, such as a powder, and the particles of the starting material can have any shape. For example, the starting material particles can be cuboids, Cuboidal, substantially spherical or spheroid, like the shape of a sheet. The particle surfaces can be smooth, rough or angular and the particles can be multi-faceted or have a single continuous curved surface. The particles can be porous or non-porous.

可藉由研磨前驅物材料，例如下述的摻雜或未摻雜矽，且然後篩分或分級該經研磨前驅物材料而得到類立方形的、多面的、像薄片的、實質上球形或類球形的起始材料。例示性的研磨方法包括粉末研磨、噴射研磨(jet milling)或球研磨。根據大小、形狀及前驅物材料的形式，不同的研磨方法可製造不同大小、形狀及表面光滑度的粒子。像薄片的粒子亦可由將前驅物材料的薄片折斷/研磨而製造。或者起始材料可由各種沉積、熱漿或雷射消熔技術製造，其係藉由將薄膜或微粒層沉積於基板上且藉由將該薄膜或微粒層從該基板移除且需要的話將其研磨至更小的粒子。 The quasi-square, multifaceted, sheet-like, substantially spherical or by grinding the precursor material, such as the doped or undoped germanium described below, and then sieving or classifying the ground precursor material Spherical starting material. Exemplary grinding methods include powder milling, jet milling, or ball milling. Depending on the size, shape and form of the precursor material, different grinding methods can produce particles of different sizes, shapes and surface smoothness. Particles like flakes can also be produced by breaking/grinding the flakes of the precursor material. Or the starting material can be made by various deposition, hot paste or laser ablation techniques by depositing a film or layer of particles on the substrate and removing the film or layer of particles from the substrate and, if desired, Grind to smaller particles.

起始材料可包含實質上相同大小的粒子。或者，該起始材料可具有粒度的分布。在兩種情況下，篩子及/或分級器可用來移除一些或所有具有在所欲大小界限之外的最大或最小大小之起始材料。 The starting material can comprise particles of substantially the same size. Alternatively, the starting material can have a distribution of particle sizes. In either case, the screen and/or classifier can be used to remove some or all of the starting materials having a maximum or minimum size outside of the desired size limits.

在柱狀粒子係藉由蝕刻含矽材料形成的情況下，該起始材料可為p-或n-型或混合物之未摻雜矽或摻雜矽，例如以鍺、磷、鋁、銀、硼及/或鋅摻雜的矽。該矽較佳具有一些摻雜，因為其提升矽在蝕刻製程間相較於未摻雜矽的導電性。該起始材料視需要為具有1019至1020載體/cc.的p-摻雜矽。 In the case where the columnar particles are formed by etching a germanium-containing material, the starting material may be p- or n-type or a mixture of undoped germanium or doped germanium, for example, germanium, phosphorus, aluminum, silver, Boron and/or zinc doped germanium. The germanium preferably has some doping because it enhances the conductivity of the germanium during the etching process compared to the undoped germanium. The starting material is optionally p-doped with 10 19 to 10 20 carrier/cc.

用來形成該柱狀粒子的矽小粒可具有90.00質量%或超過，例如95.0%至99.99%，視需要為98%至99.98%的矽純度。 The ruthenium particles used to form the columnar particles may have a purity of 90.00% by mass or more, such as 95.0% to 99.99%, and if desired, 98% to 99.98%.

起始材料可為用在半導體工業中形成小粒之相對高純度矽晶圓。或者，該等小粒可為相對低純度冶金級的矽，其係商業可得且可具有至少98%的矽純度。冶金級的矽特別適合，因為相對低的成本及相對高的缺陷密度(相較於用在半導體工業中的矽晶圓)。此係導致低阻抗且因此高 的導電性，其當該等柱狀粒子或纖維在可充電電池中用作陽極材料時係有利地。冶金級的矽中所存在的不純物可包括鐵、鋁、鎳、硼、鈣、銅、鈦及釩、氧、碳、錳及磷。某些不純物諸如Al、C、Cu、P及B可藉由提供摻雜元素進一步提升該起始材料的導電性。該矽可經如上述之研磨及分級。該矽的一個實例係來自Elkem of Norway「SilgrainTM」，其可經研磨及篩分(若需要)以製造可能為類立方形及/或類球形的矽小粒。 The starting material can be a relatively high purity tantalum wafer used to form small particles in the semiconductor industry. Alternatively, the granules can be relatively low purity metallurgical grade ruthenium which is commercially available and can have a ruthenium purity of at least 98%. Metallurgical grades are particularly suitable because of the relatively low cost and relatively high defect density (compared to tantalum wafers used in the semiconductor industry). This leads to low impedance and therefore high The conductivity, which is advantageous when the columnar particles or fibers are used as an anode material in a rechargeable battery. Impurities present in metallurgical grade niobium may include iron, aluminum, nickel, boron, calcium, copper, titanium and vanadium, oxygen, carbon, manganese and phosphorus. Certain impurities such as Al, C, Cu, P, and B can further enhance the conductivity of the starting material by providing doping elements. The crucible can be ground and classified as described above. An example of this crucible is from Elkem of Norway "SilgrainTM" which can be ground and sieved (if needed) to produce crumbs which may be cuboidal and/or spheroidal.

用來蝕刻的小粒可為晶體，例如具有晶體大小等於或大於所欲柱狀物高度的單晶或多晶。多晶小粒可包含任何數量的晶體，例如二個或更多。 The granules used for etching may be crystals, for example, single crystals or polycrystals having a crystal size equal to or greater than the height of the desired pillars. The polycrystalline granules may comprise any number of crystals, such as two or more.

雖然柱狀粒子係如上述之矽柱狀物生長製造，起始材料可包含電活性材料且可包含金屬或碳基粒子。碳基起始材料可包含軟碳、硬碳、天然及合成石墨、石墨氧化物、氟化石墨、氟間生石墨、石墨烯。 Although the columnar particles are grown as described above for the columnar column, the starting material may comprise an electroactive material and may comprise metal or carbon based particles. The carbon-based starting material may comprise soft carbon, hard carbon, natural and synthetic graphite, graphite oxide, fluorinated graphite, fluorogenic graphite, graphene.

石墨烯基起始材料可包含含有複數個堆疊石墨烯奈米板片(GNS)及/或氧化石墨烯奈米板片(ox-GNS)，有時稱作石墨奈米小板(GNP)或者奈米石墨烯小板(NGP)的粒子。NGP(或GNP)可具有至少幾奈米(例如至少2nm)的厚度及更大的高至100μm的尺寸，較佳小於40μm。包含複數個堆疊石墨烯板片的材料為石墨材料。製造石墨烯基粒子的方法包括剝蝕(exfoliation)技術(物理、化學或機械)、解聚合(unzipping)MWCNT或CNT、藉由CVD的晶膜生長及糖的還原。 The graphene-based starting material may comprise a plurality of stacked graphene nanoplates (GNS) and/or graphene oxide nanoplates (ox-GNS), sometimes referred to as graphite nanoplatelets (GNP) or Particles of nanographene platelets (NGP). The NGP (or GNP) may have a thickness of at least a few nanometers (e.g., at least 2 nm) and a size as large as 100 μm, preferably less than 40 μm. The material comprising a plurality of stacked graphene sheets is a graphite material. Methods of making graphene-based particles include exfoliation techniques (physical, chemical or mechanical), unzipping MWCNTs or CNTs, film growth by CVD, and reduction of sugars.

圖3例示的含矽粒子的核心實質上為球形，然而該粒子核心可具有任何形狀，包括實質上球形、類球形(扁圓及長球)，及不規則或規則多面形(包括實質上立方形及類立方形)。從該粒子核心表面延伸之該等柱狀物可為光滑的、粗糙的或有角的，且可為多面或具有單一連續的曲線表面。該粒子核心可為多孔或非多孔的。類立方形核心可為片狀，具有實質上小於其長度或寬度的厚度，使得該核心僅具有兩個主要表面。 The core of the cerium-containing particles illustrated in Figure 3 is substantially spherical, however the core of the particles may have any shape, including substantially spherical, spheroidal (oblate and long spheres), and irregular or regular polyhedrons (including substantial cubes). Shape and class cubic). The pillars extending from the surface of the core of the particle may be smooth, rough or angular, and may be multifaceted or have a single continuous curved surface. The particle core can be porous or non-porous. The cuboid core may be in the form of a sheet having a thickness substantially less than its length or width such that the core has only two major surfaces.

具有長度L、寬度W及厚度T的尺寸之柱狀粒子核心的縱橫比係核心的長度L與厚度T的比例(L：T)或寬度W與厚度T的比例(W：T)，其中該厚度T係作為該粒子核心的三種尺寸中最小者。在完美球形核心的例子中，縱橫比為1：1。長球或扁圓類球形、類立方形或不規則形核心較佳具有至少1.2：1，更佳至少1.5：1且最佳至少2：1的縱橫比。像片狀的核心可具有至少3：1的縱橫比。 The aspect ratio of the columnar particle core having the length L, the width W, and the thickness T is the ratio of the length L to the thickness T of the core (L: T) or the ratio of the width W to the thickness T (W: T), wherein The thickness T is the smallest of the three dimensions of the core of the particle. In the case of a perfect spherical core, the aspect ratio is 1:1. The long or oblate spheroidal, cuboid or irregular shaped core preferably has an aspect ratio of at least 1.2:1, more preferably at least 1.5:1 and most preferably at least 2:1. A sheet-like core may have an aspect ratio of at least 3:1.

在實質上為球形核心的例子中，可在核心的一或兩個半圓上提供柱狀物。在多面核心的例子中，可在核心的一或多個(包括全部)表面上提供柱狀物。例如，在片狀核心的例子中，只在該片的主要表面之一者上提供柱狀物或在兩個主要表面上皆提供柱狀物。 In the case of a substantially spherical core, the pillars may be provided on one or two semicircles of the core. In the case of a multifaceted core, the pillars may be provided on one or more (including all) surfaces of the core. For example, in the example of a sheet core, a pillar is provided only on one of the major surfaces of the sheet or a pillar is provided on both major surfaces.

該核心材料可選為相對高導電性材料，例如相較於柱狀物具有更高導電性的材料，且該核心材料的至少一個表面可維持不以柱狀物覆蓋。該導電性核心材料的至少一個暴露的表面可提供包含柱狀粒子的複合陽極層相較於所有表面都以柱狀物覆蓋的粒子更高的導電性。 The core material may be selected from a relatively highly conductive material, such as a material having a higher electrical conductivity than the pillars, and at least one surface of the core material may remain uncovered by the pillars. At least one exposed surface of the electrically conductive core material can provide a higher electrical conductivity of the composite anode layer comprising the columnar particles than the particles covered by the pillars on all surfaces.

該等矽粒子可具有小於1微米的至少一個最小尺寸。該最小尺寸較佳小於500nm，更佳小於300nm。該最小尺寸可大於0.5nm。該粒子的最小尺寸係定義為該粒子的一個元素的最小尺寸的大小，諸如桿、纖維或線的直徑、類立方形或類球形的最小直徑，或條帶、薄片或板片的最小平均厚度，其中該粒子可由桿、纖維、線、類立方形、類球形、條帶、薄片或板片本身組成，或可包含桿、纖維、線、類立方形、類球形、條帶、薄片或板片作為該粒子的結構元素。 The germanium particles can have at least one minimum dimension of less than 1 micron. The minimum size is preferably less than 500 nm, more preferably less than 300 nm. This minimum size can be greater than 0.5 nm. The minimum size of the particle is defined as the size of the smallest dimension of an element of the particle, such as the diameter of the rod, fiber or wire, the smallest diameter of the cuboid or spheroid, or the minimum average thickness of the strip, sheet or sheet. Where the particles may consist of rods, fibers, threads, cuboids, spheres, strips, sheets or sheets themselves, or may comprise rods, fibers, threads, cuboids, spheroidal, strips, sheets or plates The sheet acts as a structural element of the particle.

該等粒子較佳具有不超過100μm，更佳不超過50μm且特別不超過30μm的最大尺寸。 The particles preferably have a maximum dimension of no more than 100 μm, more preferably no more than 50 μm and especially no more than 30 μm.

可利用光學方法，例如掃描電子顯微法測量粒度。 The particle size can be measured using optical methods such as scanning electron microscopy.

較佳至少20%，更佳至少50%的矽粒子具有本文界定的最小 尺寸。粒度分布可利用雷射繞射方法測量，例如利用下列詳述的MasterSizerRTM，或光學數位成像方法。 Preferably at least 20%, more preferably at least 50% of the cerium particles have a minimum dimension as defined herein. The particle size distribution can be measured using a laser diffraction method, for example using the MasterSizer RTM detailed below, or an optical digital imaging method.

延長碳奈米結構材料 Extended carbon nanostructured materials

本發明的組成物包括至少兩個延長碳奈米結構材料。第一延長碳奈米結構材料可具有大於第二延長碳奈米結構的直徑(或最小尺寸)。第二奈米結構材料可具有相較於第一奈米結構材料更高的每單位質量的表面區塊。第一延長奈米結構材料可具有夠大的直徑使得該奈米結構係相對直且剛硬的，而第二延長奈米結構材料可具有夠小的直徑使得其在複合物內係彈性且可彎曲或彎折。該第一延長碳奈米結構的直徑(或最小尺寸)較佳係至少100nm。該第二延長碳奈米結構的直徑(或最小尺寸)較佳係小於100nm，更佳小於90nm，更佳小於80nm。該第一及第二延長碳奈米結構各自的平均厚度及平均寬度兩者較佳係小於500nm。 The composition of the present invention comprises at least two elongated carbon nanostructure materials. The first elongated carbon nanostructure material can have a diameter (or minimum dimension) that is greater than the second elongated carbon nanostructure. The second nanostructured material can have a higher surface mass per unit mass than the first nanostructured material. The first elongated nanostructure material may have a diameter large enough such that the nanostructure is relatively straight and rigid, and the second elongated nanostructure material may have a diameter small enough that it is elastic within the composite and Bend or bend. The diameter (or minimum dimension) of the first elongated carbon nanostructure is preferably at least 100 nm. The diameter (or minimum dimension) of the second elongated carbon nanostructure is preferably less than 100 nm, more preferably less than 90 nm, still more preferably less than 80 nm. Preferably, each of the first and second elongated carbon nanostructures has an average thickness and an average width of less than 500 nm.

各延長碳奈米結構材料可具有大的縱橫比，該縱橫比係最大及最小材料尺寸的縱橫比。 Each elongated carbon nanostructure material can have a large aspect ratio that is the aspect ratio of the largest and smallest material sizes.

該第一延長碳奈米結構的縱橫比較佳係在約40至180的範圍內。該第二延長碳奈米結構的縱橫比較佳在200至500的範圍內。 The aspect ratio of the first extended carbon nanostructure is preferably in the range of about 40 to 180. The aspect ratio of the second elongated carbon nanostructure is preferably in the range of 200 to 500.

延長奈米結構可選自奈米纖維及/或奈米管及薄條帶。 The extended nanostructure can be selected from the group consisting of nanofibers and/or nanotubes and thin strips.

奈米管可為單壁或多壁。用在本發明組成物的碳奈米管較佳為多壁的。奈米管的壁可為石墨烯板片。 The nanotubes can be single or multi-walled. The carbon nanotubes used in the compositions of the present invention are preferably multi-walled. The wall of the nanotube can be a graphene sheet.

奈米纖維可為固體碳纖維或可具有狹窄的中空核心，且可從堆疊石墨烯板片形成。適合的奈米纖維材料的一個實例係由Showa Denko KK.提供的VGCFRTM。 The nanofibers can be solid carbon fibers or can have a narrow hollow core and can be formed from stacked graphene sheets. An example of a suitable nanofiber material is VGCF RTM supplied by Showa Denko KK.

視需要，延長奈米結構具有範圍在3-50μm之間的中值平均長度。該第一延長奈米結構材料的長度較佳在5-30μm的範圍內。 The extended nanostructure has a median average length ranging between 3 and 50 [mu]m, as desired. The length of the first elongated nanostructure material is preferably in the range of 5-30 μm.

各延長碳奈米結構材料的表面區塊較佳不超過100m2/g且 為至少1m2/g。 The surface block of each of the elongated carbon nanostructured materials preferably does not exceed 100 m 2 /g and is at least 1 m 2 /g.

第一延長奈米結構可為具有範圍在10-20m2/g之間的表面區塊之奈米纖維。 The first extended nanostructure can be a nanofiber having a surface block ranging between 10-20 m 2 /g.

第二延長奈米結構可為具有範圍在40-80m2/g之間的表面區塊之奈米管。 The second extended nanostructure can be a nanotube having a surface block ranging between 40-80 m 2 /g.

碳奈米結構可經官能化以提升組成物內至其他組分的黏著或連接，特別是含矽粒子。例如，碳奈米管可經含氧基團(例如COOH、OH、CO)及含氮基團(例如NH2)官能化。第二延長奈米結構可為經COOH基團官能化的碳奈米管，其可促進至含矽粒子或其他電活性粒子表面的連接性。 The carbon nanostructure can be functionalized to enhance adhesion or attachment within the composition to other components, particularly ruthenium-containing particles. For example, a carbon nanotube can be functionalized with an oxygen-containing group (eg, COOH, OH, CO) and a nitrogen-containing group (eg, NH 2 ). The second extended nanostructure can be a carbon nanotube functionalized with a COOH group that promotes connectivity to the surface of the cerium-containing particles or other electroactive particles.

包括黏結劑、含矽粒子、兩種或兩種以上不同延長碳奈米結構材料及任何其他添加劑的組成物可包括量在0.25-20重量%，視需要在0.25-10wt%的範圍內之延長奈米結構材料之每一者。組成物中該兩種或兩種以上不同的延長奈米結構材料的總量可在2-25重量%，視需要3-13重量%的範圍內。 Compositions comprising a binder, cerium-containing particles, two or more different elongated carbon nanostructure materials, and any other additives may include an amount in the range of 0.25 to 20% by weight, optionally in the range of 0.25 to 10% by weight. Each of the nanostructured materials. The total amount of the two or more different elongated nanostructure materials in the composition may range from 2 to 25% by weight, optionally from 3 to 13% by weight.

碳黑 Carbon black

組成物可包含碳黑，其可以高導電微粒碳、特性為類石墨、由具有錯合組態(包括但不限於似鏈黏聚物)且具有膠體尺寸的聚合體組成為特徵。碳黑典型地係經由熱分解及部分烴的燃燒而製作。各種類型的碳黑係可得的，包括乙炔碳。商業產物的實例包括由AkzoNobel供應的Ketjen BlackRTM EC600JD或EC300J、由Cabot Corp製作的VulcanRTM XC72R、由Tokai Carbon Co.,LTD.製作的TokaBlackRTM 5500、4500、4400或4300及由Denki Kagaku Kogyo Kabushiki Kaisha製作的DenkaBlackRTM FX-35或HS-100。該組成物可包含單一類型的碳黑或一或多種碳黑類型的掺合物。該等碳黑粒子可具有範圍在10-100nm內的尺寸及超過50m2/g的表面區塊。 The composition may comprise carbon black, which may be characterized by highly conductive particulate carbon, characterized by graphite-like, composed of a polymer having a mismatched configuration including, but not limited to, a chain-like binder and having a colloidal size. Carbon black is typically produced by thermal decomposition and combustion of some hydrocarbons. Various types of carbon black are available, including acetylene carbon. Examples of commercial products include Ketjen Black RTM EC600JD AkzoNobel or supplied by a EC300J, manufactured by the Cabot Corp Vulcan RTM XC72R, by the Tokai Carbon Co., LTD., Or produced TokaBlack RTM 5500,4500,4400 and 4300 by the Denki Kagaku Kogyo Kabushiki DenkaBlack RTM FX-35 or HS-100 made by Kaisha. The composition may comprise a single type of carbon black or a blend of one or more carbon black types. The carbon black particles may have a size ranging from 10 to 100 nm and a surface block exceeding 50 m 2 /g.

包括黏結劑、含矽粒子、第一延長碳奈米結構及第二延長碳 奈米結構、碳黑添加劑及任何及他添加劑的組成物可包括量為該組成物的至少0.25重量%，及視需要小於該組成物的10wt%之碳黑(單一類型或多種類型的掺合)。該碳黑較佳係以量在總組成物的0.5wt%至4wt%的範圍內存在。具有20-40nm的平均粒度及>1000m2/g的表面區塊之Ketjen Black EC600JD作為添加劑係特別較佳。 The composition comprising a binder, cerium-containing particles, a first extended carbon nanostructure and a second extended carbon nanostructure, a carbon black additive, and any and other additives may include an amount of at least 0.25% by weight of the composition, and A carbon black (single type or types of blending) of less than 10% by weight of the composition is required. The carbon black is preferably present in an amount ranging from 0.5% by weight to 4% by weight of the total composition. Ketjen Black EC600JD having an average particle size of 20-40 nm and a surface block of >1000 m 2 /g is particularly preferred as the additive system.

石墨 graphite

除了上述延長碳奈米結構及碳黑粒子外，組成物可包含石墨粒子，例如石墨薄片。視需要，該石墨係合成石墨。 In addition to the extended carbon nanostructures and carbon black particles described above, the composition may comprise graphite particles, such as graphite flakes. The graphite is synthetic graphite as needed.

該石墨粒子的結晶長度Lc視需要為至少50nm，視需要至少100nm。具有更大結晶長度Lc的石墨為較佳，因為其可提供更高的導電性及該複合物更高的總導電性。適合的石墨粒子之商業產物可包括由Timcal Ltd製作的imrexRTM SFG6,SFG10,SFG15,KS4或KS6。 The crystallite length Lc of the graphite particles is at least 50 nm as needed, and is at least 100 nm as needed. Graphite having a larger crystal length Lc is preferred because it provides higher conductivity and higher overall conductivity of the composite. Commercial products of suitable graphite particles may include imrex RTM SFG6, SFG10, SFG15, KS4 or KS6 manufactured by Timcal Ltd.

金屬離子電池的陽極中存在的石墨可作用為活性材料。活性石墨可提供更大的充電/放電循環數而不嚴重喪失相較於活性矽的容量，其中矽可提供相較於石墨更高的容量。因此，具有含矽活性粒子及石墨活性材料兩者的電極組成物可提供金屬離子電池，例如鋰離子電池，其具有高容量及大量充電/放電循環數的優點。依據石墨材料的類型及充電/放電的情況，矽基組成物中的石墨添加劑在充電過程中可不完全鋰化且在矽基材料之上可具有可忽略或為零的電極容量貢獻度。其可優先使用來提升組成物的總導電性。 The graphite present in the anode of the metal ion battery acts as an active material. Active graphite provides a greater number of charge/discharge cycles without severe loss of capacity compared to active ruthenium, where ruthenium provides a higher capacity than graphite. Therefore, an electrode composition having both cerium-containing active particles and a graphite active material can provide a metal ion battery, such as a lithium ion battery, which has the advantages of high capacity and a large number of charge/discharge cycles. Depending on the type of graphite material and the charge/discharge conditions, the graphite additive in the ruthenium-based composition may be incompletely lithiated during charging and may have negligible or zero electrode capacity contribution above the ruthenium-based material. It can be used preferentially to increase the overall conductivity of the composition.

組成物中存在石墨，相較於其中缺乏石墨的組成物，亦可提升該組成物的漿液之塗布性質。 The presence of graphite in the composition enhances the coating properties of the slurry of the composition as compared to the composition in which graphite is absent.

可以利用雷射繞射儀測量具有D50大小為小於50微米，視需要小於25微米的粉末提供石墨粒子。 It can be measured by a laser diffraction instrument having a D 50 size of less than 50 microns, a powder of less than 25 microns as required to provide the graphite particles.

本文所使用的Dn(例如D50或D90)意指至少n%體積的材料係 從粒子形成，其具有測量類球形當量體積直徑與認證直徑相等或小於認證直徑。 As used herein, Dn (eg, D 50 or D 90 ) means that at least n% by volume of the material is formed from particles having a measured spherical equivalent volume diameter equal to or less than the certified diameter.

像片狀的粒子可具有長度、高度及厚度，其中粒子的長度和寬度各自獨立地皆平均至少為該等粒子的厚度的五倍，視需要至少十倍。石墨薄片的平均厚度可在75-300nm的範圍內。平均尺寸可從粒子樣品的SEM影像測量。 The flaky particles may have a length, a height, and a thickness, wherein the length and width of the particles are each independently at least five times the thickness of the particles, at least ten times as desired. The average thickness of the graphite flakes can range from 75 to 300 nm. The average size can be measured from the SEM image of the particle sample.

含有黏結劑、含矽粒子、石墨及任何其他添加劑的組成物可包括量在2-30wt%，視需要2-15wt%之間的石墨。 The composition containing the binder, cerium-containing particles, graphite, and any other additives may include graphite in an amount of from 2 to 30% by weight, optionally from 2 to 15% by weight.

本案發明人令人驚訝地發現到具有含有含矽粒子及石墨粒子的複合陽極之金屬離子電池可受該含矽粒子對該石墨粒子的大小比例影響。 The inventors of the present invention have surprisingly found that a metal ion battery having a composite anode containing cerium-containing particles and graphite particles can be affected by the size ratio of the cerium-containing particles to the graphite particles.

本文所描述的石墨可為包含複數個堆疊石墨烯板片的石墨烯基粒子。石墨烯基粒子可包含複數個堆疊石墨烯奈米板片(GNS)及/或氧化石墨烯奈米板片(ox-GNS)，有時稱作石墨奈米小板(GNP)或者奈米石墨烯小板(NGP)。NGP(或GNP)可具有至少幾奈米(例如至少2nm)的厚度及更大的高至100μm的尺寸，較佳小於40μm。製造石墨烯基粒子的方法包括剝蝕(exfoliation)技術(物理、化學或機械)、解聚合(unzipping)MWCNT或CNT、藉由CVD的晶膜生長及糖的還原。 The graphite described herein can be graphene-based particles comprising a plurality of stacked graphene sheets. The graphene-based particles may comprise a plurality of stacked graphene nanosheets (GNS) and/or graphene oxide nanoplates (ox-GNS), sometimes referred to as graphite nanoplatelets (GNP) or nanographite. Small plate (NGP). The NGP (or GNP) may have a thickness of at least a few nanometers (e.g., at least 2 nm) and a size as large as 100 μm, preferably less than 40 μm. Methods of making graphene-based particles include exfoliation techniques (physical, chemical or mechanical), unzipping MWCNTs or CNTs, film growth by CVD, and reduction of sugars.

黏結劑 Adhesive

可提供黏結劑以提供粒子的黏著，且在使用於金屬離子電池的例子中，用於組成物黏著於陽極電流收集器。 A binder can be provided to provide adhesion of the particles, and in the case of a metal ion battery, the composition is adhered to the anode current collector.

黏結劑材料可為聚合材料，例如聚醯亞胺、聚丙烯酸(PAA)及其鹼金屬鹽，聚乙烯醇(PVA)、聚偏二氟乙烯(PVDF)及羧甲基纖維素鈉(Na-CMC)或橡膠基黏結劑，諸如SBR。可使用不同黏結劑材料的混合物。 The binder material may be a polymeric material such as polyimine, polyacrylic acid (PAA) and its alkali metal salts, polyvinyl alcohol (PVA), polyvinylidene fluoride (PVDF) and sodium carboxymethylcellulose (Na- CMC) or rubber based adhesives such as SBR. Mixtures of different binder materials can be used.

該黏結劑可以範圍在5-30wt%的該組成物的量提供。 The binder can be provided in an amount ranging from 5 to 30% by weight of the composition.

組成物 Composition

矽粒子及碳添加劑及任何其他添加劑可以粉末或漿液的形式提供以易於混合及掺合。例如，可藉由混合矽粒子或碳添加劑與適合量的水性(例如水)及/或非水性(例如NMP)溶劑製造漿液。包含矽粒子、碳添加劑及任何其他添加劑的組成物的漿液可藉由混合所有元素與溶劑來製造，或可藉由先製造多於一種漿液，各漿液在溶液中包含一或多個別該組成物的元素，然後將個別的漿液結合在一起以製造含所有該組成物元素的漿液。個別起始材料的溶劑可相同或不同，只要當結合時其可互溶。含或不含溶劑的黏結劑材料亦可被添加且掺合至該組成物或漿液中。所得到的漿液可沉積於基板上且乾燥以移除溶劑而形成用於金屬離子電池電極的組成物。 The cerium particles and carbon additives and any other additives may be provided in the form of a powder or slurry for ease of mixing and blending. For example, a slurry can be made by mixing cerium particles or a carbon additive with a suitable amount of an aqueous (e.g., water) and/or non-aqueous (e.g., NMP) solvent. A slurry comprising a composition of cerium particles, a carbon additive, and any other additive may be made by mixing all of the elements with a solvent, or by first producing more than one slurry, each slurry comprising one or more other compositions in solution The elements are then combined together to produce a slurry containing all of the constituent elements. The solvents of the individual starting materials may be the same or different as long as they are miscible when combined. A binder material with or without solvent may also be added and blended into the composition or slurry. The resulting slurry can be deposited on a substrate and dried to remove solvent to form a composition for the metal ion battery electrode.

本案發明人已認知到若包含含有含矽電活性材料的負電極係以超過100-300充電/放電循環的高容量(例如，每公克活性材料超過500 mAh)循環，則電極複合結構應為一致地多孔且電連接及設計來在循環期間容納活性材料體積改變而沒有自該複合結構機械或電去連接該活性材料。 The inventors of the present invention have recognized that if a negative electrode system containing a ruthenium-containing electroactive material is contained in a high capacity (e.g., more than 500 mAh per gram of active material) cycle exceeding 100-300 charge/discharge cycles, the electrode composite structure should be uniform. It is porous and electrically connected and designed to accommodate a change in volume of active material during cycling without mechanical or electrical disconnection of the active material from the composite structure.

為達成此目的，複合物內的組分可具有每單位質量適中的表面區塊值。大的表面區塊可提供該活性材料更高的反應性或提升自添加劑的導電性，然而，若該等組分的表面區塊太大，固體電解質介面(SEI)層的過度形成會增加金屬離子的損失，造成週期壽命的降低及造成多孔性的降低。此外，添加劑的過度表面區塊會需要在組成物中更高的黏結劑成分以有效地結合該複合物的該等組分且將其黏結至電流收集器-期可降低總電壓容量且使在組成物中提供適合水平的多孔性係困難的。 To achieve this, the components within the composite can have a moderate surface block value per unit mass. Large surface blocks may provide higher reactivity of the active material or increase conductivity from the additive, however, if the surface blocks of the components are too large, excessive formation of the solid electrolyte interface (SEI) layer may increase the metal. The loss of ions causes a decrease in cycle life and a decrease in porosity. In addition, excessive surface patches of the additive may require higher binder components in the composition to effectively bind the components of the composite and bond it to the current collector - the period may reduce the total voltage capacity and It is difficult to provide a suitable level of porosity in the composition.

當組成物與溶劑混合以形成用來沉積該組成物至電流收集器上的漿液，具有不同形狀及變化的體積之組分的混合較佳係該漿液包含 一致的具有所有組分平均分散且具有足夠低的黏度使薄的、一致的塗層被製造。 When the composition is mixed with a solvent to form a slurry for depositing the composition onto the current collector, the mixing of components having different shapes and varying volumes is preferably such that the slurry comprises Consistently having an average dispersion of all components and having a sufficiently low viscosity allows a thin, consistent coating to be fabricated.

本案發明人發現包含具有下列性質之組成物的負電極可提供如上所述之提升的循環表現：(a)至少50wt%且不超過80wt%的活性材料，該活性材料較佳包含結構化矽粒子；(b)範圍在5-30wt%，較佳在10-20wt%之間的黏結劑；(c)量在0.25至20wt%，較佳在3-7wt%之間的包含具有不超過100nm的最小尺寸的奈米結構之第一延長碳奈米結構材料；(d)量在0.25至20wt%，更佳在2-8wt%之間的包含具有小於100nm，較佳在30-80nm之間，的最小尺寸的奈米結構之第二延長碳奈米結構材料；(e)範圍在0.25至10wt%之間，較佳0.5至4wt%之間的碳黑；(f)範圍在2-30wt%之間的石墨粒子及/或其他添加劑、填料及間隔器；(g)至少為10-80%，較佳為20-60%的多孔性。 The inventors have found that a negative electrode comprising a composition having the following properties provides an improved cyclic performance as described above: (a) at least 50 wt% and not more than 80 wt% of active material, preferably comprising structured ruthenium particles. (b) a binder ranging from 5 to 30% by weight, preferably between 10 and 20% by weight; (c) an amount of between 0.25 and 20% by weight, preferably between 3 and 7% by weight, containing no more than 100 nm a first elongated carbon nanostructure material of a minimum size nanostructure; (d) an amount between 0.25 and 20 wt%, more preferably between 2 and 8 wt%, having a thickness of less than 100 nm, preferably between 30 and 80 nm, a second elongated carbon nanostructure material of a minimum size nanostructure; (e) a carbon black ranging between 0.25 and 10 wt%, preferably between 0.5 and 4 wt%; (f) ranging from 2 to 30 wt% Graphite particles and/or other additives, fillers and spacers; (g) at least 10-80%, preferably 20-60% porosity.

其中上述組分總百分比總和為100wt%。組成物中第一及第二延長碳奈米結構(c及d)的總量較佳係在2-25wt%，特別是在3-13wt%的範圍內。第一延長碳奈米結構材料的質量對第二延長碳奈米結構材料的質量的比例較佳不超過5：1，最佳該比例係在0.1：1至5：1的範圍內，且特別是0.5：1至2：1的範圍內。 Wherein the total percentage of the above components is 100% by weight. The total amount of the first and second extended carbon nanostructures (c and d) in the composition is preferably in the range of 2 to 25% by weight, particularly in the range of 3 to 13% by weight. The ratio of the mass of the first elongated carbon nanostructure material to the mass of the second elongated carbon nanostructure material is preferably not more than 5:1, and the ratio is preferably in the range of 0.1:1 to 5:1, and It is in the range of 0.5:1 to 2:1.

該組成物較佳包含上述結構化矽粒子。本案發明人發現所有三種碳組分c、d及e在上述的重量範圍內可製造具有優異循環穩定性的負電極。在不意欲被理論限制下，咸信藉由利用延長碳奈米結構例如直徑範 圍在30-80nm之間且量如上述之MWCNT，該MWCNT可與矽結構化粒子之結構特徵纏繞以形成小範圍導電性網絡而不過度填充介於該需要用來提供矽擴充的間隔之結構特徵與電解質的途徑之空隙及間隔。該更大直徑、剛性的第一延長碳奈米結構，諸如VGCF，為更長範圍的電連接提供導電性橋且在該組成物內幫助提供強的機械架構以抵擋體積的擴充及活性材料在循環期間的收縮。咸信高度分散的碳黑可在組成物中剩下的位置提供足夠的導電性。然而，若使用任何過量碳添加劑，則黏結劑的效能可能會降低且該組成物的一致性可能降低。 The composition preferably comprises the above structured ruthenium particles. The inventors of the present invention have found that all three carbon components c, d and e can produce a negative electrode having excellent cycle stability within the above weight range. Without intending to be bound by theory, Xianxin relies on the use of extended carbon nanostructures such as diameter Between MWCNTs of between 30 and 80 nm and in an amount as described above, the MWCNTs can be entangled with the structural features of the ruthenium structured particles to form a small range of conductive networks without overfilling the structure required to provide the 矽-extended spacing. The gaps and spacing between the features and the electrolyte pathway. The larger diameter, rigid first extended carbon nanostructure, such as VGCF, provides a conductive bridge for a longer range of electrical connections and helps provide a strong mechanical structure within the composition to withstand volume expansion and active material Shrinkage during the cycle. The highly dispersed carbon black provides sufficient conductivity at the remaining locations in the composition. However, if any excess carbon additive is used, the effectiveness of the binder may be reduced and the consistency of the composition may be reduced.

可藉由混合該組成物的該等組分、溶劑及視需要一或多種面活性劑、分散劑或成孔劑，且攪拌該混合物以形該組成物。可在添加至其他組分以進行最終混合階段前，先在溶劑中混合兩種或兩種以上的組分。 然後，該組成物可沉積在基板上且乾燥使溶劑蒸發以形成多孔複合薄膜。 The composition can be formed by mixing the components of the composition, the solvent, and optionally one or more surfactants, dispersants or pore formers, and stirring the mixture. The two or more components may be mixed in a solvent before being added to other components for the final mixing stage. Then, the composition can be deposited on a substrate and dried to evaporate the solvent to form a porous composite film.

實施例Example

材料 material

組成物係以選自下列材料的組分所製備：藉由蝕刻起始矽粒子(其係從Elkem of Norway「SilgrainTM」可得)形成柱狀矽粒子，其中該起始矽粒子具有11.5-12.5微米或24.5-25.5微米的D50粒度，其係利用從Malvern Instruments Ltd.可得的MastersizerTM粒度分析儀測量。應了解所得到的柱狀粒子可具有小於起始材料的D50，例如高至2或4微米，其各別更小。 The composition is prepared from a component selected from the group consisting of: etch starting ruthenium particles (which are available from Elkem of Norway "SilgrainTM") to form columnar ruthenium particles, wherein the starting ruthenium particles have 11.5-12.5 24.5-25.5 microns or micrometers particle size D 50, from which line using Malvern Instruments Ltd. Mastersizer TM available particle size analyzer. It should be appreciated that columnar particles can be obtained starting material is less than D 50, for example up to 2 or 4 [mu] m, their respective smaller.

從Showa Denko可得的VGCF碳奈米纖維，其具有150nm的平均直徑、10-20微米的平均長度及13m2/g的表面區塊。 A VGCF carbon nanofiber available from Showa Denko having an average diameter of 150 nm, an average length of 10-20 microns, and a surface block of 13 m 2 /g.

來自CheapTubes Inc的多壁碳奈米管，其具有50-80nm的平均直徑、15-20微米的平均長度及55-75m2/g的表面區塊(下指“MWCNT”)。 Multi-walled carbon nanotubes from CheapTubes Inc, which have a mean diameter of 50-80nm, 15-20 microns and an average length of 55-75m 2 / g surface of block (refer to the "MWCNT").

從AzkoNobel可得的碳黑材料(亦即Ketjenblack® EC600-JD)，其具有1400m2/g的表面區塊及20-40nm的平均粒度。 A carbon black material (ie Ketjenblack® EC600-JD) available from Azko Nobel having a surface block of 1400 m 2 /g and an average particle size of 20-40 nm.

從Denka可得的碳黑材料(亦即Denka black)，其具有69m2/g的表面區塊及35nm的平均粒度。 A carbon black material (i.e., Denka black) available from Denka having a surface area of 69 m 2 /g and an average particle size of 35 nm.

可得自TIMCAL TIMREX ® KS4,KS6,SFG6 and SFG10的石墨，其具有如表2所給的D10、D50及D90值(利用MastersizerTM粒度分析儀測量)及BET值。 Graphite available from TIMCAL TIMREX ® KS4, KS6, SFG6 and SFG10 having D 10 , D 50 and D 90 values as measured in Table 2 (measured using a Mastersizer TM particle size analyzer) and BET values.

聚丙烯酸鈉黏結劑，下指“NaPAA”，係藉由利用碳酸鈉或氫氧化鈉部分中和商業可得聚丙烯酸PAA450K至70%的中和程度而形成。用於形成柱狀粒子的起始材料粒子之粒度分佈可藉由雷射繞射測量，其中所測量的粒子係典型地假設為球形，且其中粒度係以球形當量體積直徑(spherical equivalent volume diameter)表示，例如利用從Malvern Instruments Ltd.可得的MastersizerTM粒度分析儀測量。球形當量體積直徑係具有與所測量的粒子相同體積的球的直徑。若所有測量的粉末中的粒子具有相同的密度，則球形當量體積直徑等於球形當量質量直徑(spherical equivalent mass diameter)，其係具有與所測量的粒子之質量相同的質量之球的直徑。關於測量，粉末係典型地分散在具有與該粉末材料的折射率不同之折射率的介質中。本發明粉末的合適分散劑係水。關於具有不同大小尺寸的粉末，該粒度分析儀提供球形當量體積直徑分布曲線。 A sodium polyacrylate binder, hereinafter referred to as "NaPAA", is formed by partially neutralizing a commercially available polyacrylic acid PAA 450K to 70% neutralization with sodium carbonate or sodium hydroxide. The particle size distribution of the starting material particles used to form the columnar particles can be measured by laser diffraction, wherein the measured particle system is typically assumed to be spherical, and wherein the particle size is in a spherical equivalent volume diameter. He represents, for example, using the Malvern Instruments Ltd. Mastersizer TM available particle size analyzer. The spherical equivalent volume diameter has the diameter of the sphere of the same volume as the measured particle. If the particles in all of the measured powders have the same density, the spherical equivalent volume diameter is equal to the spherical equivalent mass diameter, which is the diameter of the sphere having the same mass as the mass of the measured particles. Regarding the measurement, the powder system is typically dispersed in a medium having a refractive index different from that of the powder material. A suitable dispersing agent for the powder of the invention is water. Regarding powders having different sizes, the particle size analyzer provides a spherical equivalent volume diameter distribution curve.

圖4A係包括前述組分各者之組成物的SEM圖像，其在該組成物的漿液形成後、沉積至銅電流收集器且蒸發該漿液溶劑形成陽極層。 4A is an SEM image of a composition comprising each of the foregoing components, after the slurry of the composition is formed, deposited to a copper current collector and evaporated to form an anode layer.

第二延長奈米結構205(其在此例子中係多壁碳奈米管)係與含矽粒子201(其在此例子中係柱狀矽粒子)纏繞。第一延長奈米結構203(在此例子中係奈米纖維)提供相對長範圍的導電性，如註記的橋接兩種矽粒子之奈米纖維203。 The second elongated nanostructure 205, which in this example is a multi-walled carbon nanotube, is entangled with the cerium-containing particles 201, which in this example are columnar cerium particles. The first elongated nanostructure 203 (in this example, a nanofiber) provides a relatively long range of conductivity, such as the noted nanofibers 203 that bridge the two bismuth particles.

奈米管提供中範圍的導電率。關於圖4B及4C，可看到奈米 管205形成延伸跨越兩種矽粒子201的橋。該等奈米管及奈米粒子亦提供介於該組成物的矽粒子及石墨薄片209提升的導電率。 The nanotubes provide a medium range conductivity. About Figures 4B and 4C, you can see the nano Tube 205 forms a bridge that extends across the two bismuth particles 201. The nanotubes and nanoparticles also provide increased conductivity of the ruthenium particles and graphite flakes 209 of the composition.

一般裝置方法1 General device method 1

SwagelokTM-類型的測試電池係利用包含含矽柱狀粒子作為活性材料之組成物的陽極，其係以塗層重13.5-15.5克矽/m2沉積至10μm厚的銅箔上、在鋁箔上的NCA陰極(Li1+xNi0.8Co0.15Al0.05O2)及在該兩個電極間的Tonen分離器。該等電極及分離器係以包含VC(伸乙烯碳酸鹽，3wt%)、FEC(氟乙烯碳酸鹽，10wt%)及CO2(0.2wt%)作為添加劑的1M之LiPF6在EC/EMC中的電解質溶液濕潤。NCA陰極的容量係比指定在1200 mAh/g操作的複合電極中的ppSi之容量大三倍。該等矽柱狀粒子係利用金屬輔助蝕刻冶金等級矽粒子(具有99.7-99.95wt%的矽純度)以形成長度為1.5-2.5μm且厚度為40-150nm的不規則形狀柱狀物，使得該等柱狀物的平均質量係總矽質量的20-40%。該等電池係以ppSi充電至1200 mAh/g且放電至2.5V的中斷電壓的方式循環。充電及放電的循環速率係C/2。電極區塊係1.13cm2。 Swagelok TM - Test cell system comprising an anode using a type of columnar particles containing silicon as the active material of the composition, which is based in a coating weight of 13.5-15.5 g Si / m 2 is deposited to a thickness 10μm copper foil on an aluminum foil An NCA cathode (Li 1+x Ni 0.8 Co 0.15 Al 0.05 O 2 ) and a Tonen separator between the two electrodes. The electrodes and separators are electrolytes of ECM in 1M LiPF6 containing VC (extended ethylene carbonate, 3 wt%), FEC (fluoroethylene carbonate, 10 wt%) and CO2 (0.2 wt%) as additives. The solution is moist. The capacity of the NCA cathode is three times greater than the capacity of ppSi specified in the composite electrode operating at 1200 mAh/g. The columnar particles are metal-assisted etching metallurgical grade cerium particles (having a germanium purity of 99.7 to 99.95 wt%) to form irregularly shaped pillars having a length of 1.5 to 2.5 μm and a thickness of 40 to 150 nm, such that The average mass of the equal pillars is 20-40% of the total mass of the crucible. The batteries were circulated in such a manner that the ppSi was charged to 1200 mAh/g and discharged to an interrupt voltage of 2.5V. The cycle rate of charging and discharging is C/2. The electrode block is 1.13 cm 2 .

裝置實施例1-2 Device Example 1-2

製備呈下列重量比之材料的組成物：70wt%柱狀矽粒子(柱狀粒子D50=11.1微米) Compositions of materials in the following weight ratios were prepared: 70 wt% columnar ruthenium particles (columnar particles D50 = 11.1 microns)

14wt%黏結劑NaPAA 14wt% binder NaPAA

4wt%石墨SFG6 4wt% graphite SFG6

12wt%由延長奈米結構、VGCF及EC600組成，如表1所示。 12wt% consists of extended nanostructure, VGCF and EC600, as shown in Table 1.

該等組成物係用來製備根據一般裝置方法的鋰離子電池。該等裝置具有如表2所示之第一、第二及第三循環效能。第n次循環效能係放電容量對先前充電容量的比例，且提供在第n次充電/放電循環時，鋰在陽極或其他電池組分中損失或保留的量的指示，例如由於SEI層的形成。 These compositions are used to prepare lithium ion batteries according to conventional apparatus methods. These devices have first, second and third cycle efficiencies as shown in Table 2. The nth cycle performance is the ratio of the discharge capacity to the previous charge capacity and provides an indication of the amount of lithium lost or retained in the anode or other battery component during the nth charge/discharge cycle, for example due to the formation of the SEI layer. .

關於圖5，比較實施例1(不包含VGCF)及比較實施例2(不包含MWCNT)中的常態化容量相較於包含MWCNT及VGCF的實施例1及2係在較低循環數開始降低。 With respect to Figure 5, the normalized capacity in Comparative Example 1 (without VGCF) and Comparative Example 2 (without MWCNT) began to decrease at lower cycle numbers compared to Examples 1 and 2 containing MWCNT and VGCF.

比較實施例3顯示在實施例1或2之前的容量降低。在不意欲被任何理論限制下，咸信此實施例中碳黑的高水平可由於碳黑的高表面區塊得到高水平的黏結劑吸收。延長碳奈米結構的結合質量對碳黑粒子的質量所給出的重量比較佳係在3：1至20：1的範圍內。 Comparative Example 3 shows the capacity reduction before Example 1 or 2. Without wishing to be bound by any theory, it is believed that the high level of carbon black in this embodiment can result in a high level of binder absorption due to the high surface area of the carbon black. Extending the bonding quality of the carbon nanostructures gives a better weight for the carbon black particles in the range of 3:1 to 20:1.

裝置實施例3-6 Device Example 3-6

製備呈下列重量比之材料的組成物：70wt%柱狀矽粒子(柱狀粒子D10=11μm,D50=21微米， D90=39μm) A composition was prepared in the following weight ratio: 70 wt% columnar ruthenium particles (columnar particles D10 = 11 μm, D50 = 21 μm, D90=39μm)

12wt%黏結劑NaPAA 12wt% binder NaPAA

6wt%石墨SFG6 6wt% graphite SFG6

12wt%由VGCF：多壁碳奈米管：EC600：Ketjenblack® EC600-JD：Denka black以4：1：1：2的比例組成。石墨係如表2所示變化。 12wt% consisting of VGCF: multi-walled carbon nanotubes: EC600: Ketjenblack® EC600-JD: Denka black is composed of 4:1:1:2. The graphite system was changed as shown in Table 2.

不同大小的石墨在效能的相似處意指石墨大小對第一及後續循環效能僅具有很小或沒有影響。 The similarity in efficiency of graphite of different sizes means that the graphite size has little or no effect on the first and subsequent cycle performance.

該等組成物係用來製備根據一般裝置方法的鋰離子電池。該等裝置具有如表2所示的第一、第二及第三循環效能。 These compositions are used to prepare lithium ion batteries according to conventional apparatus methods. These devices have first, second, and third cycle efficiencies as shown in Table 2.

圖6A描繪實施例3-6容量密度的進展，且圖6B顯示該等電池之終止電壓隨循環數的進展。終止電壓係限定為4.3V。 Figure 6A depicts the progression of the density of Examples 3-6, and Figure 6B shows the progression of the termination voltage of the cells with the number of cycles. The termination voltage is limited to 4.3V.

圖6B顯示包含SFG6的實施例5之陽極電阻增加最快。特別地，實施例6的電阻相較於包含KS4的實施例3增加較快。 Figure 6B shows that the anode resistance of Example 5 containing SFG6 increased the fastest. In particular, the resistance of Example 6 increased faster than Example 3 containing KS4.

實施例6將最高容量密度帶至超過350循環。 Example 6 brought the highest capacity density to over 350 cycles.

裝置實施例7-9 Device Examples 7-9

該等裝置係如裝置實施例3-6所描述者製備，除了柱狀矽粒 子具有11μm的D50，20μm的D90及6μm的D10，且石墨係如表3所示變化。 These devices were prepared as described in Device Examples 3-6, except that the columnar ruthenium particles had a D 50 of 11 μm, a D 90 of 20 μm, and a D 10 of 6 μm, and the graphite system was changed as shown in Table 3.

表3所測量的循環效能意指實施例9表現的提升不僅是在導致在最初的幾個循環中形成較少SEI層的SFG6的較低表面區塊。 The cycle performance measured in Table 3 means that the improvement exhibited by Example 9 is not only the lower surface block of SFG6 that results in the formation of fewer SEI layers in the first few cycles.

與關於實施例3及5相對的表現相反地，圖7A顯示包含具有11微米的D50之柱狀矽粒子SFG6的實施例9，相較於包含KS4的實施例7或8，在更大循環數下維持其容量，且圖7B顯示實施例7及8的陽極之電阻增加最快，其意指在矽粒子大小及石墨大小間的關係提供最佳表現。矽：石墨D50比例較佳係至少2：1，視需要不超過4.5：1，視需要不超過4：1，最佳係在3：1至4：1的範圍內。 Contrary to the performance relative to Examples 3 and 5, Figure 7A shows Example 9 comprising columnar cerium particles SFG6 having a D50 of 11 microns, compared to Example 7 or 8 containing KS4, at a larger number of cycles The capacity is maintained below, and Figure 7B shows that the anodes of Examples 7 and 8 have the fastest increase in resistance, which means that the relationship between the particle size of the crucible and the size of the graphite provides the best performance.矽: The graphite D50 ratio is preferably at least 2:1, no more than 4.5:1 as needed, and no more than 4:1 as needed, and the optimum is in the range of 3:1 to 4:1.

一般裝置方法2 General device method 2

SwagelokTM-類型的測試電池係利用包含含70wt%之矽柱狀粒子作為活性材料之組成物的陽極，其係以塗層重30g/m2且具有5%變化的矽沉積至10μm厚的銅箔、在鋁箔上的NCA陰極(Li1+xNi0.8Co0.15Al0.05O2)及在該兩個電極間的Tonen分離器。該等電極及分離器係以1M之重量比為95：5之LiPF6與LiBOB的電解質溶液濕潤，其係在包含體積比為1：1的FEC(氟乙烯碳酸鹽)與EMC以及3wt%的VC(伸乙烯碳酸鹽)作為添加劑的溶劑中。該等矽柱狀粒子係利用金屬輔助蝕刻冶金等級矽粒子(具有99.7-99.95wt% 的矽純度)來製備。該柱狀矽粒子具有11.5μm的D50及19.9m2/g的BET。該陽極組成物亦包含14wt%的黏結劑，其中該黏結劑係70%中和的Na-PAA，其具有分子量為450k及如表4所示的各種量的石墨添加劑SFG6。 Swagelok TM - type test cell line using a composition comprising, as an active material containing an anode 70wt% of columnar particles of silicon, which is based a coating weight of 30g / m 2 and having a 5% variation of silicon deposited to a thickness of 10μm Cu Foil, NCA cathode on aluminum foil (Li 1+x Ni 0.8 Co 0.15 Al 0.05 O 2 ) and a Tonen separator between the two electrodes. The electrodes and separators were wetted with a 1 M by weight ratio of 95:5 LiPF6 and LiBOB electrolyte solution, which contained FEC (fluoroethylene carbonate) and EMC and 3 wt% VC in a volume ratio of 1:1. (Extended ethylene carbonate) as a solvent in the additive. The columnar particles are prepared by metal-assisted etching of metallurgical grade cerium particles (having a cerium purity of 99.7 to 99.95 wt%). The columnar ruthenium particles have a D50 of 11.5 μm and a BET of 19.9 m 2 /g. The anode composition also contained 14% by weight of a binder, wherein the binder was 70% neutralized Na-PAA having a molecular weight of 450 k and various amounts of graphite additive SFG6 as shown in Table 4.

除非另有特別限定，在導電性碳添加劑混合物(Cmix)中的碳添加劑的比例係CB：MWCNT：VGCF=2：5：5，其中CB係碳黑材料EC600。Cmix的量係如表4變化。 Unless otherwise specifically defined, the ratio of the carbon additive in the conductive carbon additive mixture (Cmix) is CB: MWCNT: VGCF = 2: 5: 5, wherein the CB-based carbon black material is EC600. The amount of Cmix varies as shown in Table 4.

裝置實施例11、12及比較實施例4-8之陽極組成物的調配物係顯示於表4。該等組成物係用來製備根據一般裝置方法2的鋰離子電池。 The formulation of the anode compositions of Apparatus Examples 11, 12 and Comparative Examples 4-8 is shown in Table 4. These compositions are used to prepare a lithium ion battery according to General Apparatus Method 2.

該等電池係以固定電流及固定電壓充電至1000 mAh/g。第一循環係介於4.2及3V在C/25。後續的循環係介於4.1及3V在C/3。 The batteries are charged to 1000 mAh/g at a fixed current and a fixed voltage. The first cycle is between 4.2 and 3V at C/25. Subsequent cycles are between 4.1 and 3V at C/3.

利用在半測試電池對上鋰金屬箔的陽極塗層之不同區域來測量第一循環的損失，以排除因為陰極的損失。根據一般裝置方法2所製備的裝置具有如表4顯示的陽極導電性、陽極剝離強度及第一循環損失。 The loss of the first cycle was measured using different regions of the anode coating of the lithium metal foil on the half-test cell pair to eliminate the loss due to the cathode. The apparatus prepared according to the general apparatus method 2 had the anode conductivity, the anode peel strength, and the first cycle loss as shown in Table 4.

1.碳黑的效果 1. The effect of carbon black

關於圖8，包含含有碳黑的12wt%Cmix之實施例11顯示相較於比較實施例8提升的導電性及循環壽命，其中比較實施例8具有相同的陽極調配物，但以相等量的MWCNT及VGCF取代碳黑的存在。 With respect to Figure 8, Example 11 comprising 12 wt% Cmix containing carbon black showed improved conductivity and cycle life compared to Comparative Example 8, wherein Comparative Example 8 had the same anode formulation, but with equal amounts of MWCNT And VGCF replaces the presence of carbon black.

比較實施例6，其不具有碳黑且與比較實施例8不同處係在於各別量的石墨及延長碳材料係互換，亦顯示相較於其中存在碳黑的實施例11較差的表現。 Comparative Example 6, which does not have carbon black and differs from Comparative Example 8, in that each amount of graphite and extended carbon material are interchanged, and also shows poorer performance than Example 11 in which carbon black is present.

2.導電性碳添加劑的重量範圍 2. Weight range of conductive carbon additive

增加導電性添加劑的量會增加第一循環的鋰損失(因為該等添加劑的高表面區塊)，但亦可提升剝離強度，亦即複合陽極黏著至電流收集器。 Increasing the amount of conductive additive increases the lithium loss in the first cycle (because of the high surface area of the additives), but also increases the peel strength, ie the composite anode adheres to the current collector.

降低導電性碳的量會降低複合物的電導電性，導致更高的運轉損失，因為活性粒子在循環期間變得隔離。 Reducing the amount of conductive carbon reduces the electrical conductivity of the composite, resulting in higher loss of operation as the active particles become isolated during cycling.

關於圖9，僅包含2wt%的Cmix的實施例4顯示相較於個別包含12wt%至15wt%的Cmix之實施例11及12較差的表現。 With respect to Figure 9, Example 4, which contained only 2 wt% of Cmix, showed poorer performance compared to Examples 11 and 12, which individually contained 12 wt% to 15 wt% of Cmix.

圖10顯示包含16wt%的Cmix的比較實施例5相較於包含12wt%的Cmix的實施例11隨降低的容量較差的表現。 Figure 10 shows the performance of Comparative Example 5 containing 16 wt% Cmix compared to Example 11 containing 12 wt% Cmix with reduced capacity.

數據已常態化為在第二循環上的放電容量的值。 The data has been normalized to the value of the discharge capacity on the second cycle.

其中缺乏一或多種延長碳奈米結構及碳黑的比較實施例之SEM圖像係被發現相較於根據本發明具體實施例的裝置更多孔且更鬆弛地連接。 SEM images of comparative examples in which one or more extended carbon nanostructures and carbon black are lacking are found to be more porous and more loosely connected than devices according to embodiments of the present invention.

3.導電性碳的效果 3. The effect of conductive carbon

圖10顯示當Cmix(比較實施例7)的量設定為零，其循環表現相較於包含4wt%石墨及12wt%Cmix的實施例11之電池係更差。 Fig. 10 shows that when the amount of Cmix (Comparative Example 7) was set to zero, the cycle performance was worse than that of the battery system of Example 11 containing 4 wt% of graphite and 12 wt% of Cmix.

石墨的量較佳係在1-12wt%的範圍內(當Si為70wt%)。更大量的石墨可能會降低剝離強度。 The amount of graphite is preferably in the range of 1 to 12% by weight (when Si is 70% by weight). A larger amount of graphite may reduce the peel strength.

本發明已描述關於電活性矽為第一微粒電活性材料，然而，應了解本發明可應用至其他當完全鋰化時具有超過10%大體積膨脹或可具有大於300 mAh/g的特定容量、或可為可與鋰可逆地形成合金之金屬或半金屬的其他電活性材料中。其它例示性的電活性材料係錫、鋁、電活性化合物，包括氧化物、氮化物、氟化物、碳化物及氫化物，例如錫、鋁及矽的化合物，及其合金。 The present invention has been described with respect to electroactive hydrazine as a first particulate electroactive material, however, it will be appreciated that the invention is applicable to other specific capacities having greater than 10% bulk expansion when fully lithiated or having greater than 300 mAh/g, Or it may be in other electroactive materials that can form a metal or semimetal that reversibly forms an alloy with lithium. Other exemplary electroactive materials are tin, aluminum, electroactive compounds, including oxides, nitrides, fluorides, carbides, and hydrides, such as tin, aluminum, and antimony compounds, and alloys thereof.

本發明已描述關於可充電鋰離子電池，然而，應了解本發明可應用至除了鋰之外的其他金屬離子的金屬離子電池中，且更甚者，本發明可應用至其他能量儲存裝置，例如燃料電池。 The present invention has been described in relation to rechargeable lithium ion batteries, however, it should be understood that the present invention is applicable to metal ion batteries other than lithium, and moreover, the present invention is applicable to other energy storage devices, such as The fuel cell.

雖然本發明已用特定例示性具體實例來描述，可認知本文所揭露的特徵的各種修飾、改變及/或組合對於此項技術領域中具有通常知識者係可顯見的且不背離如下列申請專利範圍所記載的本發明之範疇。 Although the present invention has been described in terms of specific illustrative embodiments, various modifications, changes and/or combinations of the features disclosed herein are apparent to those of ordinary skill in the art and without departing from the invention The scope of the invention described in the scope.

Claims (28)

一種組成物，其包含至少50重量%之第一微粒電活性材料及3-15重量%之包含延長碳奈米結構及碳黑之碳添加劑混合物，其中，該延長碳奈米結構包含至少一種第一延長碳奈米結構材料及一種不同之第二延長碳奈米結構材料，且該延長碳奈米結構：碳黑之重量比係在3：1至20：1的範圍內。 A composition comprising at least 50% by weight of a first particulate electroactive material and 3 to 15% by weight of a carbon additive mixture comprising an extended carbon nanostructure and carbon black, wherein the elongated carbon nanostructure comprises at least one An extended carbon nanostructure material and a different second extended carbon nanostructure material, and the carbon nanostructure: carbon black weight ratio is in the range of 3:1 to 20:1. 如申請專利範圍第1項之組成物，其中該第一微粒電活性材料為含矽材料。 The composition of claim 1, wherein the first particulate electroactive material is a cerium-containing material. 如前述申請專利範圍任一項之組成物，其中該第一微粒電活性材料包含具有粒子核心及自該粒子核心延伸之電活性柱狀物之粒子。 A composition according to any one of the preceding claims, wherein the first particulate electroactive material comprises particles having a particle core and an electroactive pillar extending from the particle core. 如申請專利範圍第2項及第3項之組成物，其中該含矽粒子的該等柱狀物為矽柱狀物。 The composition of claims 2 and 3, wherein the pillars containing the cerium particles are pillars. 如申請專利範圍第4項之組成物，其中該含矽粒子的核心包含矽。 The composition of claim 4, wherein the core of the cerium-containing particles comprises cerium. 如申請專利範圍第2至5項中任一項之組成物，其中該含矽粒子基本上由n-或p-摻雜矽組成且其中該等柱狀物與核心係構成整體。 The composition of any one of claims 2 to 5, wherein the cerium-containing particles consist essentially of n- or p-doped cerium and wherein the pillars are integral with the core. 如前述申請專利範圍任一項之組成物，其中該第一延長奈米結構具有至少100nm的中數平均直徑(mean average diameter)。 A composition according to any one of the preceding claims, wherein the first extended nanostructure has a mean average diameter of at least 100 nm. 如前述申請專利範圍任一項之組成物，其中該第二延長碳奈米結構材料具有不超過90nm的中數平均直徑，視需要為範圍在40-90nm內的中數平均直徑。 A composition according to any one of the preceding claims, wherein the second extended carbon nanostructure material has a median average diameter of no more than 90 nm, optionally a median average diameter in the range of 40-90 nm. 如前述申請專利範圍任一項之組成物，其中該第一延長奈米結構：第二延長奈米結構的重量比係在2.5：1至20：1的範圍內。 A composition according to any one of the preceding claims, wherein the weight ratio of the first extended nanostructure: second extended nanostructure is in the range of from 2.5:1 to 20:1. 如前述申請專利範圍任一項之組成物，其中該等至少第一及第二延長碳奈米結構各自獨立地具有至少為50的縱橫比。 A composition according to any one of the preceding claims, wherein the at least first and second extended carbon nanostructures each independently have an aspect ratio of at least 50. 如前述申請專利範圍任一項之組成物，其中該等第一及第二碳延長 奈米結構材料係各自獨立地選自碳奈米管及碳奈米纖維。 A composition according to any one of the preceding claims, wherein the first and second carbon extensions The nanostructured materials are each independently selected from the group consisting of carbon nanotubes and carbon nanofibers. 如申請專利範圍第11項之組成物，其中該第一碳延長奈米結構材料為奈米纖維且該第二延長碳奈米結構材料為奈米管。 The composition of claim 11, wherein the first carbon extended nanostructure material is a nanofiber and the second elongated carbon nanostructure material is a nanotube. 如前述申請專利範圍任一項之組成物，其中該等至少第一及第二延長碳奈米結構材料係以總量在該組成物的0.1-15重量%的範圍內提供。 A composition according to any one of the preceding claims, wherein the at least first and second extended carbon nanostructure materials are provided in a total amount ranging from 0.1 to 15% by weight of the composition. 如前述申請專利範圍任一項之組成物，其中一或多種該等延長碳奈米結構材料具有官能化之表面，視需要為以含氮基團或含氧基團官能化之表面。 A composition according to any one of the preceding claims, wherein one or more of the extended carbon nanostructure materials have a functionalized surface, optionally a surface functionalized with a nitrogen-containing group or an oxygen-containing group. 如前述申請專利範圍任一項之組成物，其中該組成物另外包含石墨。 A composition according to any one of the preceding claims, wherein the composition additionally comprises graphite. 如申請專利範圍第15項之組成物，其中該石墨係以1-30wt%，視需要1-20wt%，視需要1-15wt%，視需要1-12wt%，視需要1-6wt%的量提供於該組成物中。 The composition of claim 15 wherein the graphite is 1-30% by weight, optionally 1-20% by weight, optionally 1-15% by weight, optionally 1-12% by weight, if necessary, 1-6wt% Provided in the composition. 如前述申請專利範圍任一項之組成物，其中組成物包含3-12重量%之碳添加劑混合物。 A composition according to any one of the preceding claims, wherein the composition comprises from 3 to 12% by weight of a carbon additive mixture. 如申請專利範圍第16或第17項之組成物，其中該石墨之微晶長度Lc視需要為至少50nm，視需要為至少100nm。 The composition of claim 16 or 17, wherein the crystallite length Lc of the graphite is at least 50 nm as needed, and optionally at least 100 nm. 如前述申請專利範圍任一項之組成物，其中該碳黑係以該組成物的至少0.5wt%，及視需要以該組成物的小於10wt%，視需要以該組成物的小於4wt%的量提供。 A composition according to any one of the preceding claims, wherein the carbon black is at least 0.5% by weight of the composition, and optionally less than 10% by weight of the composition, optionally less than 4% by weight of the composition. Quantity provided. 一種金屬-離子電池，其包含陽極、陰極及介於該陽極和該陰極間的電解質，其中該陽極包含如前述申請專利範圍任一項之組成物。 A metal-ion battery comprising an anode, a cathode, and an electrolyte interposed between the anode and the cathode, wherein the anode comprises a composition according to any one of the preceding claims. 一種漿液，其包含如申請專利範圍第1-19項中任一項之組成物及至少一種溶劑。 A slurry comprising the composition of any one of claims 1 to 19 and at least one solvent. 一種形成如申請專利範圍第20項之金屬-離子電池之方法，該方法 包含藉由將如申請專利範圍第21項之漿液沉積於導電材料且蒸發該至少一種溶劑以形成陽極之步驟。 A method of forming a metal-ion battery according to claim 20 of the patent application, the method A step of forming an anode by depositing a slurry as in claim 21 of the patent application onto a conductive material and evaporating the at least one solvent. 一種組成物，其包含第一微粒電活性材料、第一延長碳奈米結構材料及第二延長碳奈米結構材料，其中該第一延長碳奈米結構材料具有至少100nm的中數平均直徑，該第二延長碳奈米結構材料具有小於90nm的中數平均直徑，且其中該第一微粒電活性材料包含具有粒子核心及自該粒子核心延伸之電活性材料之柱狀物的粒子。 a composition comprising a first particulate electroactive material, a first elongated carbon nanostructure material, and a second elongated carbon nanostructure material, wherein the first elongated carbon nanostructure material has a median average diameter of at least 100 nm, The second elongated carbon nanostructure material has a median average diameter of less than 90 nm, and wherein the first particulate electroactive material comprises particles having a particle core and a pillar of an electroactive material extending from the particle core. 一種組成物，其包含第一微粒電活性材料、第一延長碳奈米結構材料及第二延長碳奈米結構材料，其中該第一延長碳奈米結構材料具有至少100nm的中數平均直徑，且該第二延長碳奈米結構材料具有範圍在40-90nm內的中數平均直徑。 a composition comprising a first particulate electroactive material, a first elongated carbon nanostructure material, and a second elongated carbon nanostructure material, wherein the first elongated carbon nanostructure material has a median average diameter of at least 100 nm, And the second elongated carbon nanostructure material has a median average diameter ranging from 40 to 90 nm. 一種組成物，其包含黏結劑、第一微粒電活性材料及碳添加劑，該等碳添加劑包含第一延長碳奈米結構材料、第二延長碳奈米結構材料、石墨及碳黑。 A composition comprising a binder, a first particulate electroactive material, and a carbon additive, the carbon additive comprising a first elongated carbon nanostructure material, a second elongated carbon nanostructure material, graphite, and carbon black. 一種組成物，其包含黏結劑、第一微粒電活性材料及碳奈米結構添加劑，該等碳奈米結構添加劑包含第一延長碳奈米結構材料、第二延長碳奈米結構材料及視需要碳黑，其中該碳奈米結構添加劑形成不多於10重量%之該組成物。 a composition comprising a binder, a first particulate electroactive material, and a carbon nanostructure additive, the carbon nanostructure additive comprising a first elongated carbon nanostructure material, a second extended carbon nanostructure material, and optionally Carbon black, wherein the carbon nanostructure additive forms no more than 10% by weight of the composition. 一種組成物，其包含黏結劑、第一微粒電活性材料及至少一種延長碳奈米結構材料，其中該延長碳奈米結構材料具有官能化之表面。 A composition comprising a binder, a first particulate electroactive material, and at least one extended carbon nanostructure material, wherein the extended carbon nanostructure material has a functionalized surface. 如申請專利範圍第27項之組成物，其中該組成物包含至少兩種延長碳奈米結構材料。 The composition of claim 27, wherein the composition comprises at least two elongated carbon nanostructure materials.
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